TW201501787A - Retrofit of polymer production apparatus - Google Patents

Abstract

Disclosed are retrofit processes for retrofitting a polymer production apparatus to produce a plurality of polymer products. The retrofit process may comprise modifying an existing primary manifold to include a retrofit manifold and at least one additive injection apparatus. The retrofit process may also comprise modifying an existing secondary manifold to include an additive injection line and a polymer solidifier in contact with the secondary manifold. The retrofitted polymer production apparatus produces varied finished polymer products from one continuous polymerization reactor.

Description

Reinforcement of polymer production equipment Cross-reference to related applications

The present application claims priority to U.S. Application Serial No. 61/818,239, filed on May 1, the entire entire entire entire entire entire entire entire entire entire content

The present invention is directed to a method for reinforcing a prior art polymer production unit to produce a plurality of polymerization products from a continuous polymerization unit. In particular, the present invention is directed to a method of reinforcing an existing polymer production apparatus to produce a plurality of polymeric products by allowing the injection of different additives into different portions of the liquid polymer using an additive injection device.

A wide variety of polymers are known in the art for use in the preparation of shaped articles such as films, silk tubes, tapes, and the like. The polymer, typically in the form of a solid wafer, is melted and extruded into the articles. One important class of polymers includes polyamines, which are commonly used in fabrics, garments, packaging, tire reinforcements, carpets, engineering thermoplastics for molding automotive parts, electronic equipment, sporting goods, and many industrial applications. Aliphatic polyamines, also known as nylons, can be made from dicarboxylic acids and diamines, such as solutions of salts of dicarboxylic acids and diamines. Nylon is a high performance material for plastic and fiber applications requiring special durability, heat resistance and toughness.

However, many challenges have been encountered in the processing of preparing such polymers. For example, when a shaped article is made from molten polyhexamethylene hexamethylenediamine ("nylon 6,6"), polyamine is known to decompose at a high temperature that maintains the polyamine in a molten state. Decomposition The article is discolored and tends to have an undesirable effect on the physical properties of the article. It has been proposed to solve this problem using a heat stabilizing additive added to the molten polymer, for example, U.S. Patent No. 3,121,763.

It has also been proposed to incorporate other additives into the molten polymer. U.S. Patent No. 3,824,207 proposes the injection of a pigment into a monomeric reaction mass to produce a pigmented high molecular weight polyamine. Carothers et al., U.S. Patent No. 2,119,584, shows that a quantitative amount of a polyamine aqueous solution requires the addition of a modifier to a solution which substantially dissolves the entire amount of the diamine and dicarboxylic acid. Modifiers include viscosity stabilizers, plasticizers, matting agents, pigments, and dyes.

However, the previously proposed method of incorporating additives into polymers still presents challenges. For example, as shown in WO 99/10408, injection of an additive into the polyamine polymerization process upstream of the reactor may decompose the additive.

In addition, the introduction of additives to the various stages of the polyamine polymerization process, especially upstream of the polymerization reactor, can result in significant delays in the manufacture of products that meet the desired technical requirements. The additive can be incorporated into the polymerization product using a variety of methods, such as physically mixing the additive with the polymeric nylon 6,6, causing the nylon 6,6 pellet to surface tumble with the powdered additive, or physically to the melt extruder Incorporating additives.

Manufacturers need to manufacture a variety of nylon grades from a single polymerization process and device. The precursor salt solution may comprise water and hexamethylene diammonium adipate. The precursor salt solution can be evaporated and heated to produce a polymer. Injecting an additive package, such as a salt solution, an evaporator, or at the inlet of a continuous polymerization reactor prior to polymerization, limits flexibility. For example, all of the resulting polymers contain additives that are injected into the salt solution, and thus prevent the operator from making a plurality of polymeric products. Further, in order to change the additive and the polymerization product, it takes a lot of time to switch the process and manufacture the respective salt solutions having different additives.

Conversely, there are a number of technical problems with injecting additives into the effluent of a continuous polymerization process. First, it is difficult to uniformly and uniformly distribute the additive in the polymer body. In addition, conventional injection valves tend to block. In addition, injection of additives downstream of the reactor can cause Degradation of additives.

Accordingly, there is a need for a method of reinforcing existing polymerization units to allow for the manufacture of a plurality of polymerization products from a continuous polymerization process.

In a first embodiment, the present invention is directed to a method for reinforcing a polymer production apparatus comprising: a) providing a main manifold having two openings for connecting to a polymerization reactor and a second opening for connection to the primary solidifier, and a conduit for directing the liquid polymer from the polymerization reactor to the primary solidifier; b) having a plurality of manifolds including the first manifold valve and the second manifold valve a reinforcing manifold of the valve replacing a portion of the primary manifold upstream of the second opening; c) connecting the first additive injection device to the first manifold valve; d) reinforcing the first portion of the liquid polymer from the reinforcement Manipulating the manifold to the first additive injection device; and e) injecting a first additive into the first portion of the liquid polymer to produce a first finished polymeric product comprising the first additive, wherein the first additive injection device A secondary manifold, at least one additive injection line coupled to the secondary manifold, and a polymer solidifier in fluid communication with the secondary manifold downstream of the at least one additive injection line. The reinforcing manifold can include an opening for connection to the primary solidifier. The reinforcing manifold can include an opening for connection to the polymerization reactor. The reinforcing method may further include at least one connecting pipe for fastening the reinforcing manifold to the main manifold. The reinforcing method can further include disposing a gasket between the at least one connecting tube and the main manifold, forming a substantially airtight connection between the main manifold and the reinforcing manifold. The reinforcement method can further include welding the reinforcement manifold to the primary manifold. The reinforcing manifold can have an inner diameter that is substantially similar to the primary manifold. Essentially all of the reinforcing manifold can be constructed of stainless steel. The first and second manifold valves may be cross rod injection valves, two-way valves, three-way valves, diverter valves, or combinations thereof. A plurality of manifold valves may contain from 2 to 10 manifold valves. The secondary manifold may include a pump downstream of the first manifold valve and upstream of the at least one additive injection line. The pressure of the main manifold can be from 10 MPa to 31 MPa. The pressure within the reinforcing manifold can be substantially similar to the pressure within the primary manifold. The first additive can be selected from the group consisting of heat stabilizers, defoamers, glass fibers, lubricants, copolymers, catalysts, flame retardants, plasticizers, impact modifiers, fillers, and changing the final balance. Compounds and mixtures thereof. The first additive injection device can comprise from 2 to 10 additive injection lines. The at least one additive injection line can comprise a static mixer. The first additive injection device can include an additive injection valve for connecting at least one additive injection line to a secondary manifold. When the additive injection valve is open, the at least one additive injection line can be pressurized to a higher pressure than the secondary manifold pressure. Essentially all of the portion of the additive injection valve and each of the first and second manifold valves may be constructed of stainless steel. The additive injection valve can be a cross rod injection valve, a two-way valve, a three-way valve, a diverter valve, or a combination thereof. The reinforcing method may further comprise: f) connecting the second additive injection device to the second manifold valve; g) directing the second portion of the liquid polymer from the reinforcing manifold to the second additive injection device; and h) polymerizing to the liquid A second additive is injected into the second portion of the article to produce a second finished polymeric product comprising the second additive. The second additive may be selected from the group consisting of heat stabilizers, defoamers, glass fibers, lubricants, copolymers, catalysts, flame retardants, plasticizers, impact modifiers, fillers, and changing the final balance. Compounds and mixtures thereof. The first additive and the second additive may be different. The reinforcing method may further comprise forming a liquid polymer by condensing the dicarboxylic acid with the diamine. The dicarboxylic acid may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecane. Diacid, dodecanedioic acid, maleic acid, glutaconic acid, callus acid and muconic acid, 1,2- or 1,3-cyclohexanedicarboxylic acid, 1,2- or 1, 3-benzenediacetic acid, 1,2- or 1,3-cyclohexanediacetic acid, isophthalic acid, terephthalic acid, 4,4'-oxybisbenzoic acid, 4,4-benzophenone Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, p-tert-butylisophthalic acid and 2,5-furandicarboxylic acid, and mixtures thereof. In one embodiment, the dicarboxylic acid is adipic acid. The diamine can be selected from the group consisting of ethanol diamine, trimethylene diamine, putrescine, cadaverine, hexamethylenediamine, 2-methylpentamethylenediamine, heptamethylenediamine. , 2-methylhexamethylenediamine, 3-methylhexamethylenediamine, 2,2-dimethylpentamethylenediamine, octamethylenediamine, 2,5-dimethyl Hexamethylenediamine, nonamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, decamethylenediamine, 5-methylindole Diamine, isophoronediamine, undecyldiamine, dodecamethylenediamine, 2,2,7,7-tetramethyloctamethylenediamine, bis(p-amino ring Hexyl)methane, bis(aminomethyl)norbornane, optionally substituted by one or more C ₁ to C ₄ alkyl groups, C ₂ -C ₁₆ aliphatic diamine, aliphatic polyether diamine and furan Amines such as 2,5-bis(aminomethyl)furan, and mixtures thereof. In one embodiment, the diamine is hexamethylenediamine. In some embodiments, the dicarboxylic acid and the diamine are adipic acid and hexamethylenediamine.

In a second embodiment, the present invention is directed to a method for reinforcing a polymer production apparatus comprising: a) providing a main manifold having two openings for connecting to a polymerization reactor and a second opening for connection to the primary solidifier, and a conduit for directing the liquid polymer from the polymerization reactor to the primary solidifier; b) placing a portion of the primary manifold upstream of the second opening, wherein the reinforcing manifold has a plurality of manifold valves including a first manifold valve and a second manifold valve; c) connecting the first additive injection device to the first manifold valve; d) directing the first portion of the liquid polymer from the reinforcing manifold to a first additive injection device; e) injecting a first additive into the first portion of the liquid polymer to produce a first finished polymeric product comprising the first additive; f) connecting the second additive injection device to the second manifold valve; g) directing a second portion of the liquid polymer from the reinforcing manifold to the second additive injection device; and h) injecting the second additive to the second portion of the liquid polymer to produce a second finished polymerization product comprising the second additive, among them The first and second additive injection devices each include a secondary manifold, at least one additive injection line coupled to the secondary manifold, and a polymer solidified in fluid communication with the secondary manifold downstream of the at least one additive injection line Device.

In a third embodiment, the present invention is directed to a method for reinforcing a polymer production apparatus comprising: a) providing a main manifold for directing a liquid polymer from a polymerization reactor to a primary solidifier, The primary manifold has at least one secondary manifold for injecting an additive into the primary manifold upstream of the primary solidifier; b) connecting the polymer solidifier to the at least one secondary manifold; c) at the polymer solidifier Upstream, connecting at least one additive injection line to the at least one secondary manifold; d) directing a first portion of the liquid polymer to the at least one secondary manifold; and e) flowing the liquid through the at least one additive injection line The first additive is injected into the first portion of the polymer to produce a first finished polymeric product comprising the first additive. After the first portion of the liquid polymer is directed to the at least one secondary manifold, the first additive may not be added to the primary manifold. The polymer solidifier can be directly connected to at least one secondary manifold and the polymer solidifier is not directly connected to the primary manifold. The reinforcement method can further comprise a manifold valve for regulating the flow of the first portion of the liquid polymer of the autonomous manifold to the at least one secondary manifold. The manifold valve can be a plug resistant injection valve. The manifold valve can be a cross rod injection valve, a two-way valve, a three-way valve, a diverter valve, or a combination thereof. Essentially all of the manifold valve can be constructed of stainless steel. The reinforcing method can further comprise repeating step c) to connect 2 to 10 additive injection lines to at least one secondary manifold. The at least one additive injection line can comprise a static mixer. The reinforcement method can further comprise an additive injection valve for connecting the at least one additive injection line to the at least one secondary manifold. The additive injection valve can be a plug resistant injection valve. The additive injection valve can be a cross rod injection valve, a two-way valve, a three-way valve, a diverter valve, or a combination thereof. The reinforcement method can further include adding at least one pump downstream of the manifold valve and upstream of the additive illumination valve in the at least one secondary manifold. The primary manifold may include a pressure controller that maintains the pressure within the primary manifold from 10 MPa to 31 MPa. The at least one secondary manifold may include a pressure controller that maintains a pressure within the at least one secondary manifold from 10 MPa to 28 MPa. The polymerization reactor can produce a liquid polymer by condensing a dicarboxylic acid with a diamine. The dicarboxylic acid may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecane. Diacid, dodecanedioic acid, maleic acid, glutaconic acid, callus acid and muconic acid, 1,2- or 1,3-cyclohexanedicarboxylic acid, 1,2- or 1, 3-benzenediacetic acid, 1,2- or 1,3-cyclohexanediacetic acid, isophthalic acid, terephthalic acid, 4,4'-oxybisbenzoic acid, 4,4-benzophenone Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, p-tert-butylisophthalic acid and 2,5-furandicarboxylic acid, and mixtures thereof. In one embodiment, the dicarboxylic acid is adipic acid. The diamine can be selected from the group consisting of ethanol diamine, trimethylene diamine, putrescine, cadaverine, hexamethylenediamine, 2-methylpentamethylenediamine, heptamethylenediamine. , 2-methylhexamethylenediamine, 3-methylhexamethylenediamine, 2,2-dimethylpentamethylenediamine, octamethylenediamine, 2,5-dimethyl Hexamethylenediamine, nonamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, decamethylenediamine, 5-methylindole Diamine, isophoronediamine, undecyldiamine, dodecamethylenediamine, 2,2,7,7-tetramethyloctamethylenediamine, bis(p-amino ring Hexyl)methane, bis(aminomethyl)norbornane, optionally substituted by one or more C ₁ to C ₄ alkyl groups, C ₂ -C ₁₆ aliphatic diamine, aliphatic polyether diamine and furan Amines such as 2,5-bis(aminomethyl)furan, and mixtures thereof. In one embodiment, the diamine is hexamethylenediamine. In some embodiments, the dicarboxylic acid and the diamine are adipic acid and hexamethylenediamine. The first additive may comprise a heat stabilizer, an antifoaming agent, a glass fiber, a lubricant, a copolymer, a catalyst, a flame retardant, a plasticizer, an impact modifier, a filler, and/or a compound that changes the final balance.

In a fourth embodiment, the present invention is directed to a method for reinforcing a polymer production apparatus comprising: a) providing a main manifold for directing a liquid polymer from a polymerization reactor to a primary solidifier, The primary manifold has at least one secondary manifold for injecting an additive into the primary manifold upstream of the primary solidifier; b) connecting the polymer solidifier to at least one secondary manifold; c) upstream of the polymer solidifier Connecting at least one additive injection line to at least one secondary manifold; d) placing one portion of the primary manifold upstream of the primary solidifier, wherein the reinforcing manifold has a plurality of manifold valves; e) injecting the first additive The device is coupled to the reinforcing manifold valve; f) directing the first portion of the liquid polymer to the at least one secondary manifold; g) injecting the first additive into the first portion of the liquid polymer via the at least one additive injection line, Producing a first finished polymeric product comprising a first additive, directing the first finished polymeric product to a polymer solidifier; h) directing a second portion of the liquid polymer from the reinforcing manifold to the first additive injection package And i) injecting the second additive to the second portion of the liquid polymer to produce a second finished polymerization product comprising the second additive.

1‧‧‧Polymerization

3‧‧‧Previous technical polymerization processing

4‧‧‧Previous technical polymerization processing

5‧‧‧ storage tank

6‧‧‧ pipeline

7‧‧‧Evaporator

8‧‧‧Aggregate entrance

9‧‧‧Additives

11‧‧‧ pipeline

12‧‧‧ pipeline

13‧‧‧ Additives

14‧‧‧ pipeline

15‧‧‧ pump

16‧‧‧Liquid polymer

18‧‧‧Polymer Curler

19‧‧‧Finished product

20‧‧‧polymerization reactor

21‧‧‧Main manifold

22‧‧‧ Valve

25‧‧‧Secondary manifold

26‧‧‧ pump

27‧‧‧Additive storage tank

71‧‧‧ desired location

72‧‧‧ desired location

101‧‧‧Polymerization

102‧‧‧ polymer additive device

108‧‧‧ polymer inlet

115‧‧‧Main manifold pump

116‧‧‧ polymer

118‧‧‧Polymer curing device

119‧‧‧Finished product

120‧‧‧polymerization reactor

121‧‧‧Main manifold

122‧‧‧Main manifold valve

123‧‧‧Main manifold valve

124‧‧‧Main manifold valve

125‧‧‧Secondary manifold

126‧‧‧Secondary manifold pump

127‧‧‧Additive injection storage tank

128‧‧‧Additive injection line

129‧‧‧Additive syringe pump

130‧‧‧Additive Injection Valve

131‧‧‧Liquid polymer

132‧‧‧ Additives

133‧‧‧Polymer curing device

135‧‧‧Secondary manifold

136‧‧‧Secondary manifold pump

137‧‧‧Additive injection storage tank

138‧‧‧Additive injection line

139‧‧‧Additive syringe pump

140‧‧‧Additive injection valve

141‧‧‧Liquid polymer

142‧‧‧ Additives

143‧‧‧Polymer curing device

145‧‧‧Secondary manifold

146‧‧‧Secondary manifold pump

147‧‧‧Additive injection storage tank

148‧‧‧Additive injection line

149‧‧‧Additive syringe pump

150‧‧‧Additive injection valve

152‧‧‧ Additives

153‧‧‧Polymer curing device

157‧‧‧Second additive storage tank

158‧‧‧Second additive injection line

159‧‧‧Second additive syringe pump

160‧‧‧Second additive injection valve

161‧‧‧Finished product

162‧‧‧Finished product

164‧‧‧Finished product

201‧‧‧Handle

202‧‧‧Pipe connector

203‧‧‧ check valve

204‧‧‧Supply pipeline

205‧‧‧Injection

207‧‧‧Packing shell

208‧‧‧ position

209‧‧‧ screw

210‧‧‧pipe assembly

211‧‧‧ nuts

212‧‧‧ bolt

213‧‧‧ valve body

214‧‧‧Entry埠

215‧‧ vent

216‧‧‧埠

217‧‧‧ plug

218‧‧‧ Export 埠

219‧‧‧Void area

220‧‧‧Drainage pipe

221‧‧‧drainage pipeline

The aspects of the invention are schematically illustrated by the following figures, wherein: Figure 1 is a conventional apparatus for preparing a polyamidamide polymer.

2 is a schematic illustration of a polymer additive apparatus comprising two additive injection devices in accordance with one embodiment of the present invention.

Figure 3 is a schematic illustration of a polymer additive apparatus comprising three additive injection devices in accordance with one embodiment of the present invention.

4 is a schematic illustration of the polymeric additive device of FIG. 3 with a manifold valve of the additive injection device closed in accordance with one embodiment of the present invention.

Figure 5 is a schematic illustration of a polymer additive apparatus having two additive injection lines in addition to an additive injection device in accordance with one embodiment of the present invention.

Figure 6A is a side elevational view of a crossbar polymer valve for use in accordance with an embodiment of the present invention.

Figure 6B is a side elevational view of a portion of the crossbar polymer valve of Figure 6A, used in accordance with an embodiment of the present invention.

Figure 7 is a side elevational view of an I-type polymer valve allowed to flow through an outlet, in accordance with an embodiment of the present invention.

Figure 8 is a side elevational view of an I-type polymer valve that allows flow through two outlets, in accordance with an embodiment of the present invention.

Figure 9 is a side elevational view of an I-type polymer valve allowed to flow through an outlet, in accordance with an embodiment of the present invention.

Figure 10 is a side elevational view of a Type II polymer valve that is not permitted to flow through a valve, in accordance with an embodiment of the present invention.

Figure 11 is a side elevational view of a flow-through polymer valve in an injection position for use in accordance with an embodiment of the present invention.

Figure 12 is a side elevational view of a flow guiding polymer valve in a flow guiding position for use in accordance with an embodiment of the present invention.

Figure 13 is a schematic illustration of a polymerization process that can be reinforced with a polymeric additive device in accordance with one embodiment of the present invention.

Figure 14 is a schematic illustration of a polymerization process that can be reinforced with a polymeric additive device in accordance with one embodiment of the present invention.

The terminology used herein is for the purpose of describing particular embodiments and the invention As used herein, the singular forms " It will be further understood that the term "comprising", when used in the specification, is intended to mean the presence of the features, integers, steps, operations, components and/or components, but does not exclude the presence or addition of one or more other features, integers, steps, Operations, component groups, components, and/or groups thereof.

Terms such as "including", "including", "having", "including" or "involving" and variations thereof are intended to be broad and encompass the subject matter and equivalents listed below, and additional subject matter not stated . In addition, when the composition, the component group, the processing or method steps, or any other expressions are preceded by the traditional phrase "including", "including" or "containing", it is understood that the composition also encompasses the composition, component Group, process or method step or any other expression before the narrative of the phrase "consisting essentially of", "consisting of" or "group selected from" , component group, processing or method steps or any other statement.

Where appropriate, the equivalents of the structures, materials, acts, and all components or step-plus-function elements in the claims are intended to include any structure, material, or action that is used in combination with the claimed elements. The description of the present invention has been presented for purposes of illustration and description. Many modifications and variations will be apparent to those skilled in the art without departing from the scope of the invention. The embodiments were chosen and described in order to best explain the embodiments of the invention A variety of corrections for use. Therefore, while the invention has been described in terms of the embodiments of the present invention, it will be understood that

Reference will now be made in detail to certain disclosed subject matter. It is to be understood that the scope of the invention is to be construed as being limited by the scope of the claims. To the contrary, the subject matter of the invention is intended to cover all alternatives, modifications, and equivalents, which are included within the scope of the subject matter disclosed herein.

introduction

The present invention is directed to a method of reinforcing an existing polymer production unit using the polymeric additive device described herein. The invention is also directed to a polymer additive device and a method of making a plurality of polymeric products using a polymer additive device. The polymer additive device is in fluid communication with a polymerization device comprising a continuous polymerization reactor. The polymerization apparatus may also contain a flasher and a vessel or tank for conditioning (e.g., adjusting molecular weight) the polymer. The polymeric additive device comprises a primary manifold and at least one additive injection device, such as at least two additive injection devices. The primary manifold is a distribution line that directs the liquid polymer from the polymerization unit through a polymerization reactor discharge line or a flasher feed line. In one embodiment, the primary manifold distributes the liquid polymer to a polymer processor, such as a polymer solidifier, that is in contact with the primary manifold. The primary manifold may include a primary manifold valve for controlling the flow of liquid polymer into the additive injection device.

The additive injection device includes a secondary manifold that can carry at least a portion of the liquid polymer. The secondary manifold can be in contact with at least one additive injection line for feeding the secondary manifold with an additive in combination with the liquid polymer. The process can be operated continuously and is advantageous in allowing more than one polymerization product to be produced by one continuous process. Generally, the method includes forming a liquid polymer, removing the liquid polymer from the polymerization device, and directing at least two portions of the liquid polymer to the respective additive injection devices to produce different polymerization products.

The present invention proposes a significant improvement over the prior art because it allows for productivity, production The amount and amount of liquid polymer are maximized while also allowing for tailored end products. For example, the liquid polyamine can be separated into portions and the various portions can be combined with different additives. The first part can be combined with a flame retardant additive, the second part can be combined with a pigment, and the third part can be combined with a heat stabilizer. Thus, three polyamine products were prepared from one liquid polyamine. In another example, the first portion of the liquid polymer is fed to the polymer processor to form a primary finished polymer product, and the other portion is sent to an additive injection device to form a finished polymer product comprising the additive. Furthermore, the present invention is advantageous because it reduces contamination in the polymerization apparatus that may be caused by accumulation of additives. Since the additive can be added after the polymer leaves the polymerization unit, the polymerization unit does not need to be exposed to the additive.

The invention also includes controlling the additive injection line pressure to be higher than the secondary manifold pressure when the additive valve is open. By controlling the pressure using a suitable injection valve, the injection valves are capable of preventing the polymer from flowing back to the additive injection line as the additive stream is shut off. In the absence of pressure control, temperature may be affected and the injection valve and tubing will require heat tracing as the temperature drop will cure the polymer and block the device.

The present invention overcomes this drawback by providing manufacturers with the flexibility to manufacture a plurality of polymeric products from a single polymerization unit comprising a single polymerization reactor. The continuous polymerization reactor can produce multiple products simultaneously or at a time, depending on the requirements of the established plant or operator. The present invention avoids the problems associated with introducing additives into the main manifold. The device also enables the manufacture of polyamines that meet the technical requirements of a given polyamine product in a very short period of time relative to previously existing devices and methods. The number of different products that can be made in a single polymerization unit that utilizes one polymerization reactor combined with one or more additive injection devices is only limited by economics. The process of the invention can also be upgraded to provide flexibility in delivering a variety of polymeric products.

Liquid polymer and its preparation

The liquid polymer is removed from the polymerization unit through a manifold as described above. The liquid polymer removed from the polymerization unit may be free of additives. In another embodiment, the liquid polymer removed from the polymerization unit can comprise an additive. However, liquid polymer composition self-polymerizing device After removal, the additive is not added to the liquid polymer as it is in the main manifold. The liquid polymer can be any polymer in liquid form, including molten polymers or polymers in flowable form. For the purposes of the present invention, a polymer is a liquid polymer when it is in liquid form at the polymerization reactor temperature. Exemplary liquid polymers can include polyamines, polyolefins, polyurethanes, polyesters, polystyrenes, and polycarbonates. In a preferred embodiment, the invention is directed to the manufacture of polyamines.

The polyamine used in the process of the invention may be obtained from a single monomer, or a mixture of two or more different monomers, such as dicarboxylic acids and diamines, which initially react to form poly(hexamethylenehexamethylenediamine). amine). Therefore, in the case of poly(hexamethylene hexamethylenediamine), the main monomers are hexamethylenediamine and adipic acid. Such polyamines derived from two different monomers are generally produced using a solution obtained by mixing a stoichiometric amount of a dicarboxylic acid with a diamine in a solvent such as water. In one embodiment, the molar ratio of adipic acid to hexamethylenediamine may range from 0.8:1 to 1.2:1. The concentrated salt solution is typically removed by evaporation. The polyamine is obtained by evaporating the salt solution by heating under high temperature and high pressure while avoiding the formation of any solid phase to avoid solidification of the mixture. The relative molar amount of adipic acid to hexamethylenediamine can vary depending on the desired end product.

In some embodiments, the liquid polymer can be a condensation product of a dicarboxylic acid monomer and a diamine monomer.

The dicarboxylic acid suitable for the present invention is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, suberic acid, azelaic acid, and azelaic acid. Acid, undecanedioic acid, dodecanedioic acid, maleic acid, glutaconic acid, callus acid and muconic acid, 1,2- or 1,3-cyclohexanedicarboxylic acid, 1, 2- or 1,3-benzenediacetic acid, 1,2- or 1,3-cyclohexanediacetic acid, isophthalic acid, terephthalic acid, 4,4'-oxybisbenzoic acid, 4,4 - benzophenone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, p-tert-butylisophthalic acid and 2,5-furandicarboxylic acid, and mixtures thereof. In one embodiment, the dicarboxylic acid monomer comprises at least 80% adipic acid, such as at least 95% adipic acid.

Adipic acid (AA) is the best dicarboxylic acid and is used in powder form. AA is generally obtained in pure form containing very low levels of impurities. Typical impurities include less than 60 ppm of other acids (monobasic acids and less dibasic acids), nitrogenous materials, trace metals such as iron (less than 2 ppm) and other heavy metals (less than 10 ppm), arsenic (less than 3 ppm), and hydrocarbon oils ( Less than 10ppm).

A diamine suitable for the present invention is selected from the group consisting of ethanol diamine, trimethylene diamine, putrescine, cadaverine, hexamethylenediamine, 2-methylpentamethylenediamine, and seven Methylenediamine, 2-methylhexamethylenediamine, 3-methylhexamethylenediamine, 2,2-dimethylpentamethylenediamine, octamethylenediamine, 2 , 5-dimethylhexamethylenediamine, nonamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, decamethylenediamine, 5-methylindolediamine, isophoronediamine, undecyldiamine, dodecamethylenediamine, 2,2,7,7-tetramethyloctamethylenediamine, double (Aminocyclohexyl)methane, bis(aminomethyl)norbornane, optionally C ₂ -C ₁₆ aliphatic diamine substituted by one or more C ₁ to C ₄ alkyl groups, aliphatic polyether Diamines and furan diamines, such as 2,5-bis(aminomethyl)furan, and mixtures thereof. The selected diamine may have a higher boiling point than the dicarboxylic acid, and the diamine is preferably not xylylenediamine. In one embodiment, the diamine monomer comprises at least 80% hexamethylenediamine, such as at least 95% hexamethylenediamine. Hexamethylenediamine (HMD) is most commonly used to make nylon 6,6. The HMD cures at about 42 ° C, and water is usually added to suppress this melting temperature and to simplify the treatment. Thus, HMD is commercially available as a concentrated solution, for example from 80% to 100% or from 92% to 98% by weight.

In the following description, the terms adipic acid (AA) and hexamethylenediamine (HMD) will be used to denote dicarboxylic acids and diamines. However, this method also applies to the other dicarboxylic acids and other diamines indicated above. Further, in the following description, the terms nylon 6,6 and polyamine will be used to denote a liquid polymer. However, this method is also applicable to other liquid polymers as shown above.

In addition to polyamines based solely on dicarboxylic acids and diamines, it is sometimes desirable to incorporate other monomers. When added in a proportion of less than 20% by weight, for example less than 15% by weight, such monomers may be added to the nylon salt solution without departing from the invention. The third starting substance may include a single official Carboxylic acid, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, undecanoic acid, lauric acid, myristic acid, nutmeg oil Acid, palmitic acid, palmitoleic acid, hexadecenoic acid, stearic acid, oleic acid, elaidic acid, isooleic acid, linoleic acid, erucic acid and the like. These may also include indoleamines such as alpha-acetalamine, alpha-propionamide, beta-propionamide, gamma-butyrolactam, delta-valeramine, gamma-valerene Amines, caprolactam and similar indoleamines. These may also include lactones such as alpha-lactone, alpha-propiolactone, beta-propiolactone, gamma-butyrolactone, delta-valerolactone, gamma-valerolactone, caprolactone and Similar to lactones. These may include difunctional alcohols such as monoethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2-ethylhexane-1,3-diol (etohexadiol), pair Methane-3,8-diol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. Higher functional molecules such as glycerol, trimethylolpropane, triethanolamine and the like are also suitable. Also suitable for hydroxylamine, such as ethanolamine, diethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 3-amino-1-butene Alcohol, 2-amino-1-butanol, 4-amino-2-butanol, pentanolamine, hexanolamine and the like. It will be understood that blends of any such monomers may also be utilized without departing from the invention.

Many additives can be used in embodiments of the invention. These additives can be injected using the additive injection line of the present invention. Preferably, this allows the incorporation of the additive into a portion of the liquid polymer. Additives can include heat stabilizers such as any of copper salts, potassium iodide, or other antioxidants known in the art. Such additives may also include polymerization catalysts such as metal oxides, acidic compounds, metal salts of oxygenated phosphorus containing compounds or other additives known in the art. The additives may also be matting agents and color formers such as titanium dioxide, carbon black or other pigments, dyes and colorants known in the art. The additives used may include antifoaming agents such as cerium oxide dispersions, polyoxy oxycopolymers or other antifoaming agents known in the art. Lubricating acids such as zinc stearate, stearyl erucamide, stearyl alcohol, aluminum distearate, ethyl bis-stearylamine or known in the art may be used. He is a polymer lubricant. A nucleating agent may be included in the mixture, such as fumed ceria or alumina, molybdenum disulfide, talc, graphite, calcium fluoride, phenylphosphinate or other acids known in the art. Other common additives known in the art, such as flame retardants, plasticizers, impact modifiers, and some types of fillers may also be added to the molten unbalanced mixture prior to curing. It will be appreciated that blends of any of these additives may also be utilized without departing from the basic principles of the embodiments disclosed herein. In one embodiment, the additives and blends thereof include, but are not limited to, copper plasticizers, matting agents, pigments, dyes, copper-based stabilizers, pigments including colorless pigments, glass, fiberglass, lubricants Copolymers such as nylon 6, nylon 6, 10 and nylon 6, 12, catalysts, and compounds that alter the final equilibrium (e.g., final amine). In some embodiments, the additive is provided in the form of a masterbatch. In some aspects, the same additive can be injected into multiple injection lines, but can be combined with another additive, in varying amounts or a combination thereof.

The polymeric product described herein may comprise from 0.1% to 20% by weight of additives, such as from 0.5% to 20% by weight, from 1% to 20% by weight, from 1% to 15% by weight or from 1% to 10% by weight of additives. . Depending on the additives and amounts to be added to the portion of the liquid polymer, the additives may be maintained at a temperature of from 40 ° C to 300 ° C, such as from 50 ° C to 270 ° C, from 60 ° C to 250 ° C or from 80 ° C to 220 ° C. It will be appreciated that the amount of additive and the temperature of the additive are adjusted to maintain the polymer flowing through the device. Thus, the temperature of the additive can be below 40 °C, such as at ambient temperature. The polymeric product may have a molecular weight of from 10,000 to 50,000 Daltons, such as from 12,000 to 45,000 Daltons or from 10,000 to 20,000 Daltons.

The liquid polymer can be prepared from a polymer salt solution, such as a nylon salt solution or a nylon salt that has been subjected to water removal (eg, evaporation). The nylon salt solution can be made according to the target salt content and the target molar ratio of the dicarboxylic acid (e.g., AA) to the diamine (e.g., HMD). The target molar ratio can be calculated by measuring the pH of the nylon salt solution. A nylon salt solution can be formed in a continuous stirred tank reactor (CSTR) by feeding AA powder to the CSTR and by separately feeding HMD and water (alone or in combination) into the CSTR. AA powder can be fed to CSTR based on volume or weight in. Due to the need to form a nylon salt solution with low variability with respect to the target salt content and pH, the AA powder can be metered using a weight loss feeder based on weight. It has been found that metering AA powder using a weight loss feeder results in a lower variability in target salt concentration and pH in the nylon salt solution, as the bulk density of the AA powder can vary greatly. In an exemplary embodiment of the invention, the change in the low variable feed rate relative to the target feed rate may be less than ± 5%. Acceptable weight loss feeders may include Acrison Models 402/404, 403, 405, 406, and 407; Merrick Model 570; K-Tron Models KT20, T35, T60, T80, S60, S100, and S500; and Brabender FlexWall® Plus and FlexWall® Classic.

Polymer additive method

A prior art process for preparing a polymer having an additive is shown in FIG . The polymerization process 1 comprises storing a prepolymer solution, also referred to as a polymer salt solution, in a storage tank 5 . When a sufficient polymer salt solution is produced, or when it is additionally desired to form a polymer, the polymer salt solution is transferred through evaporator 7 through line 6 to form a polymer salt which is then transferred to polymerization reactor 20 via polymerization inlet 8 . Polymer 16 is removed from reactor 20 and sent to a solidifier 18 to produce a finished polymeric product 119 . Additives can be added to two different portions of the polymerization process 100 as needed. In one embodiment, additive 9 is added to storage tank 5 via line 11 . In another embodiment, additive 9 is added to line 6 via line 12 as the polymer salt solution is passed to polymerization reactor 20 . In another embodiment (not shown), an additive 9 is added to the liquid polymer 16 . In another embodiment, in addition to or instead of the additive 9 9 additive, the additive 13 is added to the liquid polymer 16 via line 14. However, when the liquid polymer is continuously produced in the reactor 20 , each of these methods produces a polymerization product.

The polymerization process 101 of the present invention is shown in Figures 2 , 3 and 4 and includes a polymer additive device 102 . Polymerization process 101 includes a polymer salt storage tank 105 , an evaporator 107 , a transfer line 106 , a polymerization reactor 120, and a polymer inlet 108 . The polymer inlet 108 comprises a polymer salt and any monomer added to adjust the stoichiometry of the polymer salt, the inlet feeding the polymer salt into the polymerization reactor 120 . The polymeric salt may optionally comprise an additive as described above. The polymer salt is polymerized in a continuous polymerization reactor 120 to form a polymer 116 in a condensation reaction. Polymer 116 is transferred from polymerization reactor 120 into main manifold 121 , through pump 115 and into polymer additive unit 102 . Prior to exiting polymerization reactor 120 , polymer 116 can be fed to a flasher (not shown) and/or a vessel (not shown) for adjusting the molecular weight of the polymer. The container can include a mixing basket and a screw pump. The container can be horizontal or vertical and can be operated under vacuum. The polymer additive device 102 includes a main manifold 121 , a main manifold pump 115 , a polymer solidifier 118, and main manifold valves 122 and 123 . The polymer additive device 102 also includes at least one, for example at least two, additive injection devices. As shown in FIG. 2, comprises a secondary manifold 125, and 135, pump 126 and the secondary manifold 136, and 127 inject the additive reservoir 137, line 128 and 138 inject the additive, the additive injection pump 129 and 139, the additive injection valve The two additive injection devices 130 and 140 and the polymer solidifiers 133 , 143 are in fluid communication with the main manifold 121 . The finished polymeric products 161 , 162 and 119 are then removed from the polymer solidifiers 133 , 143 and 118 . Although a pump, valve, and injection line are shown in Figures 2 , 3, and 4 , additional pumps, valves, and injection lines, as well as temperature controllers and sensors, pressure controllers and sensors, and, where appropriate, exist. Static mixer.

The invention allows the manufacture of a plurality of polymeric products. The invention also allows for improved and/or replacement of effective additive injection devices. In conventional processing, in order to switch from the first additive to the second additive and the second additive to produce the polymerization product, the processing can take from 3 to 12 hours. The time requirement is due to the physical switching of the equipment (additive storage tank) to remove all liquid polymers comprising the first additive, to add the second additive and to produce a polymeric product comprising the desired amount of the second additive. Preferably, the process of the present invention switches the first additive to the second additive within one hour, such as within 30 minutes, within 15 minutes, within 5 minutes, or within 1 minute, and produces a polymeric product comprising the desired amount of the second additive.

In some embodiments, the finished polymeric product 119 can be substantially free of additives. In some embodiments, the finished polymeric product 119 in the additive injection reservoir 127 and/or additive storage tank 137 can be substantially free of additives. The additive in the additive injection storage tank 127 may be an additive different from the additive in the additive storage tank 137 . Furthermore, more than one additive may be stored in the additive storage tank in the form of an additive mixture. Each of the finished polymeric products 161 , 162, and 119 can be a different finished polymeric product.

Polymer 116 flows through primary manifold 121 and secondary manifolds 125 and 135 at a temperature sufficient to maintain the polymer in liquid form. In some embodiments, for polyamines, the temperature of the liquid polymer can range from 265 °C to 300 °C. In the main manifold 121 , the pressure may be 10 to 31 megapascals (MPa). The pressure in each of the secondary manifolds may be equal to or less than the pressure in the primary manifold, such as 10 MPa to 31 MPa, or 10 MPa to 28 MPa. The primary and secondary manifolds may be jacketed or heated or insulated to maintain the temperature of the primary and secondary manifolds in a manner that maintains the polymer in liquid form. Additionally, the primary manifold and the secondary manifold may each include a temperature controller to measure the temperature of the liquid polymer and adjust the temperature as needed. The primary manifold and the secondary manifold may each also include a pressure controller to measure and adjust the pressure of the liquid polymer.

And the main manifold 123 when the valve 122 as shown in FIG 2 is opened between the main manifold 121 and the secondary manifold 125, and 135 to provide fluid communication. The inner diameter of the main manifold 121 may be equal to or greater than the inner diameter of the secondary manifolds 125 and 135 . In some embodiments, the inner diameter of the secondary manifold relative to the inner diameter of the primary manifold 121 can be used to control the flow and pressure of the liquid polymer in the secondary manifold.

Although the primary manifold 121 in the manifold is shown to have a 90° angle, the primary manifold 121 can be a straight tube, a curved tube, or an elbow from the continuous polymerization reactor 120 or can be at any suitable angle to the continuous polymerization reactor 120. Angled.

The primary and secondary manifolds may have a circular, elliptical, rectangular or any other suitable cross-section depending on the requirements of each installation and processing. In one embodiment, the primary manifold can be a cylindrical tube. The inner diameter of the main manifold 121 may vary from 25 mm to 650 mm, such as from 50 mm to 300 mm or from 50 mm to 200 mm. The inner diameter of the secondary manifolds 125 and 135 can vary from 25 mm to 300 mm, such as from 50 mm to 250 mm or from 50 mm to 150 mm. For a primary or secondary manifold, "inner diameter" means the longest inner diameter of the section of the primary or secondary manifold, regardless of the shape of the manifold. The primary manifold 121 can include a corrosion resistant material that limits the dissolution of iron into the polymer. Examples include austenitic stainless steels such as 304, 304L, 316 and 316L. Secondary manifolds 125 and 135 may comprise materials similar to those used for the primary manifold. Although the secondary manifolds 125 and 135 are shown at an angle of 90° relative to the main manifold 121 , they may be bent, bent, or may be angled with the main manifold 121 at any suitable angle. Moreover, although secondary manifolds 125 and 135 are shown as being parallel and on the same side of primary manifold 121 , they may be located on opposite sides of the primary manifold 121 or otherwise arranged.

Each of the secondary manifold and additive injection lines may optionally be equipped with one or more static mixers (not shown) to ensure uniform mixing. An exemplary static mixer is further described in Perry, Robert H. and Don W. Green. Perry's Chemical Engineers' Handbook . 7th ed. New York: McGraw-Hill, 1997: 18-25 to 18-34, which is incorporated by reference. The way is incorporated in this article.

The additive injection reservoir can be used to store additives supplied as pure liquid, molten pure solids, liquid masterbatch or solid masterbatch. Each additive storage tank may include suitable means for maintaining the additive supply container at the desired temperature, as desired. In some embodiments, the additive is stored at a temperature that is substantially the same as the temperature at which the liquid polymer passes into the secondary manifold. For example, if the liquid polymer 116 is at a temperature of 300 ° C, the additive storage tank 127 can be maintained at a temperature of about 300 ° C using a heating device as it enters the secondary manifold 125 . The additive storage tank may be capable of maintaining and adjusting temperature using a heat transfer tube jacket, electric heat tracing, fabric insulation heating, a jacketing device, a band heater, or an electric heating. If a heat transfer tube is used, a suitable heat transfer fluid such as a mixture of biphenyl and biphenyl oxide (sold by Dow Chemical Company under the trade name DOWTHERM® A) can be used. These devices can also be used to jacket and/or heat the primary and secondary manifolds, as well as the primary manifold valves and additive injection valves.

In other embodiments, the temperature of the additive in the additive injection line can range from 40 °C to 300 °C. The additive can be selected based on the amount of additive added to the liquid polymer The temperature. For example, if the finished polymeric product will comprise 0.1% by weight of additives, the additive temperature will have minimal effect on the liquid polymer and the additive can be injected at different temperatures (eg, below the temperature of the liquid polymer in the secondary manifold). In the secondary manifold.

Additive injection lines 128 and 138 are pressurized to provide an additive having a higher pressure than liquid polymers 131 and 141 . This helps improve the mixing of the additive with the liquid polymer and prevents the additive from flowing back to the additive storage. When the polymer additive device 102 is initially used, the additive injection line is brought to the target pressure prior to opening the additive injection valve. Subsequently, the main manifold valve is opened to allow liquid polymer to flow through the secondary manifold. The additive injection valve is then opened and the additive is pumped through the valve into the secondary manifold. The pressure of the liquid polymer in the secondary manifold can range from 10 MPa to 31 MPa. In some embodiments, the additive injection line pressure can be at least 2 to 10% greater than the liquid polymer pressure in the secondary manifold.

In some embodiments, as shown in FIG. 4 and FIG. 3, the device 102 comprises a polymer additive three valves 122, 123 and 124, when it opens in the main manifold 121 and the secondary manifold 125, 135 and 145 of Provide fluid communication between. It will be appreciated that depending on the number of polymeric products that the polymeric additive device 102 requires to be manufactured, the device may include more than three valves and additive injection devices, such as four or more, five or more, or six or more. In some embodiments, the polymeric additive device 102 comprises from 3 to 10 additive injection devices. The secondary manifold 145 includes a secondary manifold pump 146 , an additive injection reservoir 147 , an additive injection line 148 , an additive injection pump 149 , an additive injection valve 150 , a polymer solidifier 153, and a finished polymerization product 164 .

In Figure 2 , main manifold valves 122 and 123 are shown in an open position, such as fully open or partially open to allow flow through the valve, and additive injection valves 130 and 140 are shown in an open position. Thus, liquid polymer 116 flows through primary manifold 121 to secondary manifolds 125 and 135 and to polymer solidifier 118 . In addition, because additive injection valves 130 and 140 are shown in an open position, and additives flow from additive storage tanks 127 and 137 into secondary manifolds 125 and 135 .

In Figure 3 , main manifold valves 122 , 123, and 124 are shown in an open position and additive injection valves 130 , 140, and 150 are shown in an open position. Therefore, the liquid polymer 116 flows through the main manifold 121 . At least a portion of the liquid polymer 116 flows into the secondary manifolds 125 , 135, and 145 . At least a portion of the liquid polymer 116 flows into the polymer solidifier 118 . In addition, additive injection valves 130 , 140, and 150 are shown in an open position, and thus additives flow from additive storage tanks 127 , 137, and 147 into the secondary manifold. The liquid polymer with additives 132 , 142, and 152 is then fed to polymer solidifiers 133 , 143, and 153 through secondary manifolds 125 , 135, and 145 .

In Figure 4 , main manifold valves 122 and 123 are shown in an open position and additive injection valves 130 and 140 are shown in an open position. Main manifold valve 124 and additive injection valve 150 are shown in a closed position. Therefore, the liquid polymer 116 flows through the main manifold 121 . At least a portion of the liquid polymer 116 flows into the secondary manifolds 125 and 135 but does not flow into the secondary manifold 145 . In addition, because additive injection valves 130 and 140 are shown in an open position, and thus additives flow from additive storage tanks 127 and 137 into secondary manifolds 125 and 135 . The liquid polymer with additives 132 and 142 is then fed to polymer solidifiers 133 and 143 through secondary manifolds 125 and 135 .

In FIG. 5 , the secondary manifold 145 includes a second additive storage tank 157 , a second additive injection line 158 , a second additive injection pump 159, and a second additive injection valve 160 . The additive in the additive storage tank 157 is different from the additive in the additive storage tank 147 . Although two different additive storage tanks are shown in the secondary manifold 145 , it should be understood that any and/or all of the secondary manifolds may have more than one additive injection line, as well as additive pumps, valves, and others required to operate the additive injection line. element. Main manifold valves 122 , 123, and 124 are shown in an open position and additive injection valves 130 , 140, and 150 are shown in an open position. Therefore, the liquid polymer 116 flows through the main manifold 121 . At least a portion of the liquid polymer 116 flows into the secondary manifolds 125 , 135, and 145 . At least a portion of the liquid polymer 116 flows into the polymer solidifier 118 . In addition, additive injection valves 130 , 140 , 150, and 160 are shown in an open position, and thus additives flow from additive storage tanks 127 , 137 , 147, and 157 into the secondary manifold. The liquid polymer with additives 132 , 142, and 152 is then fed to polymer solidifiers 133 , 143, and 153 through secondary manifolds 125 , 135, and 145 .

The primary manifold pump 115 and the secondary manifold pumps 126 , 136, and 146 may be pumps selected from the group consisting of: vane pumps, piston pumps, flexure pumps, multi-leaf pumps, gear pumps, centrifugal pumps, rings Piston pump and screw pump.

A main manifold valve 122, 123 and 124, and the additive injection valve 130, 140, 150 and 160 may comprise an injection valve clogging resistance, such as FIGS. 6A and 6B illustrate cross bar of the injection valve, FIG. 7, FIG. 8, FIG. 9 and the type I and / or II type polymer valve illustrated in Figure 10 , and the flow guide valve illustrated in Figures 11 and 12 . Although the functions of the various valves are described as appearing as additive injection valves, each valve can also be used as a primary manifold valve that, when opened, allows liquid polymer to flow into the secondary manifold or shuts off the flow of liquid polymer into the secondary manifold.

As shown in FIGS. 6A and 6B in FIG., The injection valve comprising a cross bar body 213, a handle 201, packing casing 207, whereby a portion of the liquid polymer flows through the injection port of the secondary manifold 205, and the conduit 209 includes a screw Assembly 210 . The tubing assembly 210 includes a supply line 204 through which the additive is transferred to the valve. Line assembly 210 is inserted into the bottom of the valve at location 208 . The tubing assembly 210 includes a check valve 203 that only allows flow in one direction. Line connector 202 connects the two lines. The package 207 is held in place by the nut and bolt assemblies 211 , 212 to prevent leakage.

As shown in Figure 7, also known as Type I polymer valve two-way valve allowing liquid polymer to flow into the valve gap region 219, and then allowing the two ports of an open. The Type I polymer valve has an inlet port 214 and an outlet port 218 , and a plug 217 . The inlet 214 opens to allow the additive to flow into the secondary manifold. The outlet crucible 218 runs an additive plus liquid polymer flowing through the secondary manifold. The plug 217 rotates to keep one turn open (partial or complete) and the other closed. In Figure 7 , 埠218 is open and 埠214 is closed. The additive cannot be injected through the crucible 214 and the liquid polymer flows through the valve. As shown, the valve is jacketed. Heat is transferred to the valve via the crucible 216 . The vent 215 can be connected to a vacuum to remove non-condensable gases. Drain pipe 220 removes condensate and any other liquid. The Type I polymer valve can also be used as a primary manifold valve to allow the liquid polymer autonomous manifold to flow to the secondary manifold.

As FIGS. 8, 9 and 10, the polymer type II also known as three-way valve the valve, allowing the liquid polymer flow into the valve gap region 219 and then allow i) ports 214 and 218 are open (FIG. 8) , ii) 埠218 is open and 埠214 is closed ( Fig. 9) , or iii) 埠214 and 218 are both closed (Fig. 10 ). Type II polymer valves can be used as primary manifold valves to allow liquid polymer autonomous manifolds to flow to the secondary manifold.

The diverter valve is shown in Figures 11 and 12 . FIG diverter valve 11 for injection as shown by the position, wherein the liquid polymer to flow through a plane perpendicular to the gap region 219 of the injection of additives. Additives can flow through the inlet 214 . As shown, the inlet 214 can flow to line 221 by a mechanical guide member 12. The diverter valve can be used as a primary manifold valve or as an additive injection valve.

Each of the valves described herein and all portions thereof are resistant to clogging and are constructed of stainless steel.

The polymer solidifiers 133 , 143 , 153, and 118 may include a wet rotary machine, a dry rotary machine, a melt rotary machine, an extrusion rotary machine, a direct rotary machine, a gel rotary machine, an electric rotary machine, or a granulator. Each of the polymer curators 133 , 143 , 153, and 118 can be a different polymer solidifier depending on the final desired polymer product. Each polymer can be a fiber grade polymer and/or can be subsequently separated into substantially solid wafers, such as flakes or pellets.

Reinforcement of prior art polymerization processes

The present invention is directed to a reconstitution process for reconfiguring existing polymerization processes to use the polymer additive devices described herein. Prior art polymerization process 3 is shown in FIG . This processing introduces a prepolymer or a polymer salt into the polymerization reactor 20 via the inlet 8 . The liquid polymer 16 is withdrawn from the polymerization reactor 20 into the main manifold 21 , which serves as a conduit for directing the liquid polymer from the polymerization reactor 20 into the polymer solidifier 18 . In the polymerization process 3 , the main manifold 21 is the only manifold present in the process. The main manifold 21 has two openings: an opening for connection to the discharge line of the polymerization reactor 20 and an opening for connection to the polymer solidifier 18 . The polymerization process 3 may comprise a pump 15 as appropriate . Prior to the introduction of the prepolymer or polymer salt into the inlet 8 , the prior art polymerization process 3 may include additional steps and equipment to prepare the prepolymer or polymer salt for polymerization. These steps may include a salt forming reactor, an evaporator, a prepolymerization reactor, a prepolymer/gas separation, a flasher, and the like. As shown therein, the liquid polymer 13 after leaving the polymerization reactor 20, a polymerization process wherein 3 to no additive. The liquid polymer 16 flows through the main manifold 21 to the polymer solidifier 18 and recovers the finished polymeric product 19 .

The prior art polymerization process 3 can be reinforced with a polymer additive device by modifying the main manifold 21 . Reinforcement processing can include replacing a portion of the main manifold 121 that is connected upstream of the opening of the polymer solidifier 18 with a reinforcing manifold. The reinforcing manifold can be added by cutting the primary manifold 21 at the desired locations 71 and 72 and welding the reinforcing manifold into the primary manifold 21 . It should be understood that these locations can be selected based on the existing master manifold 21 position, length, and machining configuration. The reinforcing manifold includes a plurality of manifold valves including a first manifold valve and a second manifold valve. In some embodiments, the reinforcing manifold can include from 2 to 10 manifold valves. The reinforcing manifold may include at least one connecting tube for securing the reinforcing manifold to the main manifold 21 . The connecting pipe may be a press fitting, a threaded connecting pipe, a hole connector, a luer integral lock ring, or the like. Gasket may be disposed between the at least one connecting pipe to the main manifold 21, form a substantially airtight connection between the main manifold 21 and the manifold reinforcement. In addition, the reinforcing manifold can be fastened to the main manifold. Use nuts, bolts, screws or other connecting members.

The reinforcing manifold can have a shape and an inner diameter that are substantially similar or equal to the main manifold 21 . Essential portions of the reinforcing manifold, manifold valve, and additive injection valve may be constructed of stainless steel, such as austenitic stainless steels such as 304, 304L, 316, and 316L. The manifold valve can be a primary manifold valve as described herein, including a crossbar injection valve, a two-way valve, a three-way valve, a diverter valve, or combinations thereof. The pressure and temperature of the liquid polymer in the reinforcing manifold are substantially the same as the temperature and pressure in the main manifold 21 , such as a temperature of 65 ° C to 300 ° C and a pressure of 10 MPa to 31 MPa.

The reinforcing process may further comprise connecting the first additive injection device to the first manifold valve, directing the first portion of the liquid polymer from the replenishing valve to the first additive injection device, and injecting the first additive to the first portion of the liquid polymer The first finished polymerization product comprising the additive is produced. As FIG. 2, FIG. 3, FIG. 5 and FIG. 4, the additive injection means comprises a first secondary manifold 125, the secondary manifold pump 126, the injection additive storage tank 127, line 128 inject the additive, the additive injection pump 129 An additive injection valve 130 and a polymer solidifier 133 in fluid communication with the secondary manifold 125 downstream of the additive injection line 128 . The additive in the additive injection storage tank 127 can be selected from the group consisting of: defoaming agent, lubricating agent, nucleating agent, flame retardant, plasticizer, impact modifier, glass fiber, copper-based stabilizer , lubricants, matting agents, copolymers, catalysts, compounds that alter the final balance, and mixtures thereof. Additional additives may include pigments and dyes. The additive injection line 128 can further comprise a static mixer (not shown). The finished polymeric products 161 and 119 are then removed from the polymer solidifiers 133 and 118 . Each of the finished polymeric products 161 and 119 can be a different finished polymeric product.

The reinforcing method can further comprise connecting the second additive injection device to the second manifold valve, directing the second portion of the liquid polymer from the reinforcing manifold to the second additive injection device, and injecting into the second portion of the liquid polymer The second additive is to produce a second finished polymeric product comprising the second additive. As FIG. 2, FIG. 3 and FIG. 4 and FIG. 5, the second additive injection means comprises secondary manifold 135, the secondary manifold pump 136, the injection additive storage tank 137, line 138 inject the additive, the additive injection pump 139 An additive injection valve 140 and a polymer solidifier 143 in fluid communication with the secondary manifold 135 downstream of the additive injection line 128 . The additive in the additive injection storage tank 137 can be selected from the group consisting of heat stabilizers, defoamers, glass fibers, lubricants, copolymers, catalysts, flame retardants, plasticizers, impact modifiers, and fillers. Agents, compounds that alter the final balance, and mixtures thereof. In one embodiment, the additive in the first additive injection device is different than the additive in the second additive injection device. The additive injection line 138 can further comprise a static mixer (not shown). The finished polymeric products 161 , 162 and 119 are then removed from the polymer solidifiers 133 , 143 and 118 . Each of the finished polymeric products 161 , 162, and 119 can be a different finished polymeric product.

The reinforcing process may further comprise adding or modifying the pump 15 of Figures 13 and 14 . If the pump 15 does not exist, it can be added. If the pump material is not sufficient for use with the desired liquid polymer, or if the pump is not of the desired pump type, the pump 15 can be replaced with a pump 115 as described herein. In general, pump 115 can be a vane pump, a piston pump, a flexure pump, a multi-leaf pump, a gear pump, a centrifugal pump, a ring piston pump, or a screw pump.

As shown in FIG. 14, similar to the prior art polymerization process 4 and 3 prior art polymerization process, but the prior art for a polymerization process comprising 4 from polymeric additive storage tank 27, 25 of the liquid 21 in the main manifold via a secondary manifold Sub-manifold 25 of the injection additive. The primary manifold 21 optionally includes a valve 22 that can be opened or closed to control the flow of additive from the secondary manifold 25 into the primary manifold 21 . Secondary manifold 25 includes pump 26 as appropriate .

The prior art polymerization process 4 can be reinforced with a polymer additive device by modifying the primary manifold 21 and the secondary manifold 25 . Reinforcing processing can include connecting the polymer solidifier to the secondary manifold 25 and connecting at least one additive injection line to the secondary manifold 25 upstream of the polymer solidifier (now referred to as the primary polymer solidifier). The reinforcing process can further comprise directing the first portion of the liquid polymer to the secondary manifold 25 and injecting the first additive to the first portion of the liquid polymer via the at least one additive injection line. The liquid polymer comprising the additive can then be directed to the additive polymer solidifier to produce a first finished polymer comprising the first additive. The additive polymer solidifier can be directly connected to the secondary manifold. The additive polymer solidifier in contact with the secondary manifold is therefore not connected to the primary manifold 21 . In the reinforcement process, after a portion of the liquid polymer flows into the secondary manifold, the process is reinforced and the first additive is no longer injected into the main manifold 21 , but flows into the secondary manifold 25 and the additive polymer solidifier. It should be understood that while prior art polymerization process 4 shows only one secondary manifold 125 , if additional secondary manifolds are present, each may be reinforced as described herein.

If the primary manifold 21 in prior art polymerization process 4 does not contain a manifold valve or if the valve is not sufficient for reinforcement polymerization processing, the valve may be added or replaced. Described herein are materials suitable for valves and valves. Additionally, suitable materials for the additive injection line are described herein. If the secondary manifold 25 of the prior art polymerization process 4 does not include the pump 26 , a pump can be added.

Additive injection lines, additive injection reservoirs, valves, pumps, and static mixers are added as described above. Additionally, more than one additive injection line can be added to the secondary manifold 125 , for example, from 2 to 10 additive injection lines and respective additive storage tanks, valves, pumps, and static mixers.

The prior art of the polymerization process may further comprise reinforcing means 4 shown in Figure 2 of generating a reinforcing additive injection apparatus main manifold 21, or with two reinforcing additive injection devices generating a main manifold 21 as in FIG. 3 and FIG. 4 The device shown. As described for the reinforcement of prior art polymerization process 3, the reinforcement process for adding an additive injection device includes replacing a portion of the main manifold upstream of the polymer solidifier with a reinforcing manifold having a reinforced manifold valve, the additive injection device A retentive manifold valve is coupled and a portion of the liquid polymer is directed to the additive injection device to produce a finished polymeric product.

Instance Example 1

A continuous polymerization product comprising nylon 6,6 was produced. The continuous polymerization product flows through the main manifold at a temperature of 265 ° C to 300 ° C and a pressure of 10 MPa to 31 MPa. The primary manifold is in fluid communication with the two secondary manifolds via two primary manifold valves. Each of the main manifold valves opens to allow a portion of the liquid polymer to flow through each of the secondary manifolds at a temperature of 265 ° C to 300 ° C and a pressure of 10 MPa to 31 MPa. Each secondary manifold is in fluid communication with a different additive injection line. Each additive injection line is in fluid communication with an additive source. To prepare the nylon 6,6 polymer containing the additive, the additive is introduced from the additive storage tank to the additive injection line. The pressure of the additive in the additive injection line is increased to the pressure of the liquid polymer flowing through the secondary manifold. The temperature of the additive in the additive injection line can range from 40 °C to 300 °C. The additive injection valve is then opened. The target finished polymerization product is set and in order to achieve this goal, an additive in a value ranging from 0.1% by weight to 20% by weight is allowed to flow through the additive injection valve and combined with the liquid polymer in the secondary manifold.

The liquid polymer with the additive is then fed to the polymer solidifier for rotation or granulation The polymer is polymerized and the finished polymer product is recovered. Additionally, at least a portion of the liquid polymer is sent to a polymer solidifier in fluid communication with the main manifold and the finished nylon 6,6 polymer is recovered. Thus, at least two different finished nylon 6,6 polymers are recovered from the device. The time between the supply of the additive to the additive injection line and the removal of the nylon 6,6 polymer containing the additive to the target additive level was 1 hour.

Example 2

A continuous polymerization product was produced as in Example 1 and an additive was added as in Example 1. The primary manifold is in contact with three secondary manifolds, each of which is connected to a different additive injection line. Blocking the curing agent in contact with the main manifold results in no final polymerization product in the curing unit. A first additive comprising a matting agent is injected into the first secondary manifold through a first additive injection line and combined with the liquid polymer to form a polymerization product. A second additive comprising glass fibers is injected into the second secondary manifold through a second additive injection line and combined with the liquid polymer to form a polymerization product. The additive injection valve connecting the third additive injection line and the third secondary manifold is closed. The final polymerization product is produced by feeding each product through a polymer solidifier in contact with the respective secondary manifold. The process thus produces three polymerization products from a continuous polymerization process: a polymerization product A is prepared with a delustering agent, a polymerization product B is obtained from glass fibers, and a polymerization product C is obtained without using an additive. Since no additives or liquid polymers are refluxed from the respective secondary manifolds into the main manifold, the polymerization products A and C are free of glass fibers and the polymerization product B does not contain a matting agent.

Example 3

A continuous polymerization product was produced as in Example 1 and an additive was added as in Example 1. The primary manifold is in contact with three secondary manifolds, each of which is connected to a different additive injection line. A first additive comprising 20 meq/kg of final amine is injected into the first secondary manifold through a first additive injection line and combined with the liquid polymer to form a polymerization product. A second additive comprising 40 meq/kg of final amine is injected into the second secondary manifold through a second additive injection line and combined with the liquid polymer to form a polymerization product. Contains 60 meq/kg of final amine The third additive is injected into the third secondary manifold through a third additive injection line and combined with the liquid polymer to form a polymerization product. The final polymerization product is produced by feeding each product through a polymer solidifier in contact with the respective secondary manifold. The process thus produces three polymeric products from a continuous polymerization process: each having a different final amine content and thus each having a different dyeability. Dyes and/or pigments may be added downstream of the polymerization product or added by the end user.

Example 4

The continuous polymerization product was made as in Example 1 and the additive was added as in Example 1, the primary manifold being in contact with three secondary manifolds, each of which was connected to a different additive injection line. A first additive comprising nylon 6 is injected into the first secondary manifold through a first additive injection line and combined with the liquid polymer to form a polymerization product. A second additive comprising nylon 6,12 is injected into the second secondary manifold through a second additive injection line and combined with the liquid polymer to form a polymerization product. A third additive comprising nylon 6,10 is injected into the third secondary manifold through a third additive injection line and combined with the liquid polymer to form a polymerization product. The final polymerization product is produced by feeding each product through a polymer solidifier in contact with the respective secondary manifold. The process thus produces three polymeric products from one continuous polymerization process, each having a different final polymer.

Example 5

A continuous polymerization product was produced as in Example 1 and an additive was added as in Example 1. The primary manifold is in contact with three secondary manifolds, each of which is connected to a different additive injection line. A first additive comprising a lubricant is injected into the first secondary manifold through a first additive injection line and combined with the liquid polymer to form a polymerization product. A second additive comprising a copper-based stabilizer package is injected into the second secondary manifold through a second additive injection line and combined with the liquid polymer to form a polymerization product. A third additive comprising a flame retardant is injected into the third secondary manifold through a third additive injection line and combined with the liquid polymer to form a polymerization product. The final polymerization product is produced by feeding each product through a polymer solidifier in contact with the respective secondary manifold. The process thus produces three polymeric products from a continuous polymerization process: The polymerized product A of the slip agent comprises a copper-based stabilizer-encapsulated polymerized product B and a polymerized product C comprising a flame retardant.

Example 6

A continuous polymerization product was produced as in Example 1 and an additive was added as in Example 1. The primary manifold is in contact with three secondary manifolds, each of which is connected to a different additive injection line. A first additive comprising a first amount of nylon 6 is injected into the first secondary manifold through a first additive injection line and combined with the liquid polymer to form a polymerization product. A second additive comprising a second amount of nylon 6 (different from the first amount) is injected into the second secondary manifold through a second additive injection line and combined with the liquid polymer to form a polymerization product. A third additive comprising a third amount of nylon 6 (different from the first or second amount of nylon 6) is injected into the low velocity sub-manifold through a third additive injection line and combined with the liquid polymer to form a polymerization product. The final polymerization product is produced by feeding each product through a polymer solidifier in contact with the respective secondary manifold. The process thus produces three polymeric products from a continuous polymerization process, each containing varying amounts of nylon 6.

Comparison example A

The continuous polymerization product comprising nylon 6,6 is obtained by using an additive at a temperature of 265 ° C to 300 ° C and a pressure of 10 MPa to 31 MPa. A nylon salt solution is formed prior to entering the polymerization reactor. The nylon salt solution is then sent to an evaporator to remove water and then sent to the polymerization reactor. An additive is added to the solution before it is sent to the evaporator. The target finished polymerization product is set and this is achieved, and an additive having a value in the range of 0.1% by weight to 20% by weight is added to the nylon salt solution. The time between the supply of the additive to the nylon salt solution and the removal of the nylon 6,6 polymer comprising the additive to the target additive level is from 8 to 12 hours. If a second polymerization product differing from the first polymerization product is required, the polymerization unit is taken offline and cleaned to remove any accumulation from the evaporator, the polymerization reactor, the conduit between the evaporator and the reactor, and the reactor discharge line. Additives. It takes an additional 8 to 12 hours after cleaning to produce a second polymerization product that meets the target technical requirements.

Compare example B

The continuous polymerization product comprising nylon 6,6 is obtained by using an additive at a temperature of 265 ° C to 300 ° C and a pressure of 10 MPa to 31 MPa. A nylon salt solution is formed before entering the evaporator to remove water and before entering the polymerization reactor. The nylon salt solution is then sent to a storage tank for storage until needed. The target finished polymerization product is set and this is achieved, and an additive having a value in the range of 0.1% by weight to 20% by weight is added to the nylon salt solution in the storage tank. The time between providing the additive to the nylon salt solution in the storage tank and removing the nylon 6,6 polymer containing the additive to the target additive content is 8 to 12 hours. If a second polymerization product different from the first polymerization product is required, the polymerization unit is taken offline and cleaned from the storage tank, the evaporator, the polymerization reactor, the piping between the storage tank and the evaporator, the evaporator and the reactor. The intervening pipe, and the reactor discharge line remove any accumulated additives. It takes an additional 8 to 12 hours after cleaning to produce a second polymerization product that meets the target technical requirements.

Comparative example C

A continuous polymerization product comprising nylon 6,6 was produced. The continuous polymerization product flows through the main manifold at a temperature of 265 ° C to 300 ° C and a pressure of 10 MPa to 31 MPa. The primary manifold is in fluid communication with the additive injection line. The target finished polymerization product is set and in order to achieve this goal, an additive in a value ranging from 0.1% by weight to 20% by weight is allowed to flow through the additive injection line, and the liquid polymer is combined in the main manifold. The time between supplying the additive to the main manifold in the storage tank and removing the nylon 6,6 polymer containing the additive to the target additive content is 3 to 6 hours. If a second polymerization product of an additive different from the first polymerization product is desired, the polymerization unit is taken offline and the main manifold is cleaned to remove any accumulated additives from the autonomous manifold. It takes an additional 3 to 6 hours after cleaning to produce a second polymerization product that meets the target technical requirements.

Although the present invention has been described in detail, modifications in the spirit and scope of the invention will be apparent to those skilled in the art. All publications and references mentioned above are incorporated herein by reference. Moreover, it should be understood that aspects of the invention and numerous embodiments are cited The examples and portions of the various features may be combined or interchanged in whole or in part. As will be appreciated by those skilled in the art, in the foregoing description of the various embodiments, the embodiments of the other embodiments may be combined as appropriate. In addition, those skilled in the art will understand that the foregoing description is by way of example only and is not intended to limit the invention.

101‧‧‧Polymerization

102‧‧‧ polymer additive device

108‧‧‧ polymer inlet

115‧‧‧Main manifold pump

116‧‧‧ polymer

118‧‧‧Polymer curing device

119‧‧‧Finished product

120‧‧‧polymerization reactor

121‧‧‧Main manifold

122‧‧‧Main manifold valve

123‧‧‧Main manifold valve

125‧‧‧Secondary manifold

126‧‧‧Secondary manifold pump

127‧‧‧Additive injection storage tank

128‧‧‧Additive injection line

129‧‧‧Additive syringe pump

130‧‧‧Additive Injection Valve

131‧‧‧Liquid polymer

132‧‧‧ Additives

133‧‧‧Polymer curing device

135‧‧‧Secondary manifold

136‧‧‧Secondary manifold pump

137‧‧‧Additive injection storage tank

138‧‧‧Additive injection line

139‧‧‧Additive syringe pump

140‧‧‧Additive injection valve

141‧‧‧Liquid polymer

142‧‧‧ Additives

143‧‧‧Polymer curing device

161‧‧‧Finished product

162‧‧‧Finished product

Claims (15)

A method for reinforcing a polymer production apparatus, comprising: a) providing a main manifold having two openings, a first opening for connection to a polymerization device and a second opening for connection to a primary curing device, and for Directing the liquid polymer from the polymerization unit to the conduit of the primary solidifier; b) replacing the upstream of the second opening with a reinforcing manifold having a plurality of manifold valves including a first manifold valve and a second manifold valve a portion of the primary manifold; c) connecting the first additive injection device to the first manifold valve; d) directing the first portion of the liquid polymer from the reinforcing manifold to the first additive injection device; e) injecting a first additive into the first portion of the liquid polymer to produce a first finished polymeric product comprising the first additive, wherein the first additive injection device comprises a secondary manifold, at least one connected to the An additive injection line of a stage manifold, and a polymer solidifier in fluid communication with the secondary manifold downstream of the at least one additive injection line; and wherein the first additive is selected from the group consisting of: defoaming Agents, lubricants, nucleating agents, flame retardants, plasticizers, impact modifiers, glass fibers, copper-based stabilizers, lubricants, matting agents, copolymers, catalysts, compounds that change the final balance And mixtures thereof. The reinforcing method of claim 1, wherein the reinforcing manifold comprises an opening for connection to the primary solidifier and an opening for connection to a polymerization reactor discharge line. The reinforcing method of claim 1, further comprising at least one connecting pipe for fastening the reinforcing manifold to the main manifold. The reinforcing method of claim 3, further comprising a gasket disposed between the at least one connecting pipe and the main manifold to form a gap between the main manifold and the reinforcing manifold It is essentially airtight. The reinforcement method of claim 1, further comprising welding the reinforcement manifold to the primary manifold; wherein the reinforcement manifold has an inner diameter substantially similar to the primary manifold. The reinforcing method of claim 1, wherein the first and second manifold valves are cross rod injection valves, two-way valves, three-way valves, diverter valves, or a combination thereof. The reinforcing method of claim 1, wherein the plurality of manifold valves comprise 2 to 10 manifold valves. A method of reinforcement according to claim 1, wherein the secondary manifold comprises a pump downstream of the first manifold valve and upstream of the at least one additive injection line. The reinforcing method of claim 1, wherein the pressure of the main manifold is 10 MPa to 31 MPa and wherein the pressure in the reinforcing manifold is substantially similar to the pressure in the main manifold. The reinforcing method of claim 1, wherein the first additive injection device comprises 2 to 10 additive injection lines and wherein the at least one additive injection line comprises a static mixer. The reinforcing method of claim 1, wherein the first additive injection device comprises an additive injection valve for connecting the at least one additive injection line to the secondary manifold; and further wherein the additive injection valve is a cross rod injection valve, Valve, three-way valve, diverter valve or a combination thereof. The reinforcing method of claim 11, wherein the at least one additive injection line is pressurized to a pressure higher than the secondary manifold pressure when the additive injection valve is opened. The reinforcing method of claim 11, wherein the reinforcing manifold, substantially all of the portion of the additive injection valve, and each of the first and second manifold valves comprise stainless steel. The reinforcing method of claim 1, further comprising: f) connecting a second additive injection device to the second manifold valve; g) guiding the second portion of the liquid polymer from the reinforcing manifold to the second Add to And the h) injecting a second additive into the second portion of the liquid polymer to produce a second finished polymeric product comprising the second additive. The method of claim 14, wherein the second additive is selected from the group consisting of a heat stabilizer, an antifoaming agent, a glass fiber, a lubricant, a copolymer, a catalyst, a flame retardant, a plasticizer, and an impact resistance. A modifier, a filler, a compound that alters the final equilibrium, and mixtures thereof; and wherein the first additive is different from the second additive.