CN85106980A

CN85106980A - Glass fibre enhanced vinyl chloride polymer products and preparation technology thereof

Info

Publication number: CN85106980A
Application number: CN198585106980A
Authority: CN
Inventors: 道格拉斯·布鲁斯·拉里格
Original assignee: BF Goodrich Corp
Current assignee: Goodrich Corp
Priority date: 1984-07-13
Filing date: 1985-09-16
Publication date: 1987-04-01

Abstract

Hate strong vinylchlorid (VC) resin with glass fibre.This fiber is with special aminosilane coupling agent and contain the processing of alkylene oxide membrane-forming agent, and one of its effect is to make polymkeric substance VC chain produce allylic chlorine atom.The VC resin contains the capacity stablizer, stops this atom to generate, but the growing amount of this atom is enough to make it and the aminosilane reaction near the glass fibre, makes fiber and combining of resin firm that matrix material only can be damaged by cohesive failure.This material wet tenacity approximates or is higher than the dry strength of the same material of fiber surface treatment agent film former-free.

Description

Glass fibre enhanced vinyl chloride polymer products and preparation technology thereof

Theme of the present invention is to handle aspect the physics strength property improving organic synthetic resin, strengthens ryuron (being called for short " VC homopolymer ") with glass fibre.More particularly, the present invention relates to thermoplastic glass fibre enhanced (" GFR ") polyvinyl chloride (" PVC ") homopolymer and chlorinated polyvinyl chloride (" CPVC "), be exactly general hard PVC and hard CPVC here with them respectively or be referred to as " VC " homopolymer.

At present existing a large amount of GFR thermoplastic materials comprise polyolefine, polyacetal resin, polymeric amide (nylon), polycarbonate, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene (ABS) (ABS) multipolymer and new polyvinyl chloride.These glass fibre enhanced polymkeric substance can use with various form, wherein main are generally garden sphere or the elliposoidal molded pellets that thermoforming machine is used, number such as particulate diameters greatly about 3mm in the 8mm scope.So-called " thermoforming " is meant and utilizes heat and pressure that thermoplastic resin is made useful shape.Typical thermoforming process has: injection molding, the extrusion moulding of hot resin injection mould, pull out moulding, hot calender moulding, cast molding and vacuum forming or the like.The short glass fiber feeding shaper of length less than about 6.4mm, in shaper, high degree of agitation and strong shear flow make fiber further broken, often make its length reduce by 10～100 times.Like this, glass fibre plays reinforced composite, it would be better to say that it mainly has been that the effect of putting more energy into (is seen Encyclopedia of chemical Tech-nology by kirk ﹠amp; Othmer, Pg 973, Vol 13 Third Ed.John Wiley ﹠amp; Sous, 1981).The present invention relates to strengthen GFR PVC and CPVC matrix material, be not only the dry strength of strengthening them, and strengthen its wet tenacity.

Because the interchangeable heat plastic resin of output maximum is a polyvinyl chloride in the world at present, and All the time for many years, in the meantime, other resin above-mentioned has successfully come into operation after strengthening with glass fibre, suffer inappropriate like this delaying so glass fiber-reinforced polyvinyl chloride comes out on market smoothly, it seems it is the mistake in a kind of epoch.On lighter degree, this also is correct for chlorinated polyvinyl chloride, it has been widely used for the pipe that hot-fluid, particularly corrosive liquid in order to conveying belt pressure are manufactured in extrusion moulding, and is used for injection molding and manufactures various pipe fittings, pump housing or the like.

Face the task that the glass fiber-reinforced vinyl chloride resin of commercial acceptable is provided, people set about relaxing the state that it comes out and incured loss through delay very soon on market.Someone finds that the thermostability of polyvinyl chloride is relatively poor, and the glass fibre (for example, account for resin and glass gross weight 10%) that promptly uses lower aq is when strengthening, very big viscosity is also arranged, even this makes it be difficult to fill up each corner of less mould.

For overcoming the shortcoming of poor heat stability, in vinyl chloride resin, once mixed various stablizers.For reducing viscosity, a lot of solutions were once proposed, wherein the most rational is to seek and select variously perhaps can mate the suitable multipolymer of blend with vinyl chloride resin.For example, at United States Patent (USP) 2,572, disclosed polyvinyl chloride in 798,2,773,851 and 3,883,473 with the coumarone-indene resin blend.At United States Patent (USP) 3,164, openly put down in 563 glass fibre is mixed a kind of traditional technology in the various resins.

It mainly is effect for the dehydrochlorination that overcomes them that stablizer is used for the vinylchlorid molded resin, and the process of this dehydrochlorination is accelerated being higher than the second-order transition temperature of resin (" Tg ") time, and violent especially when being higher than its fusing point.Recognize fully in the prior art, this dehydrochlorination meeting of vinyl chloride resin causes producing near the Cl atom in the vinylchlorid chain link two keys and (sees in Polymer Stabilization one book after the 126th page in " Thermal Degradafion and Slabilization " chapter, W.Lincoln Hankins work, Wiley Intersciece 1972).This Cl is called " allylic Cl " (" ally-lic cl "), and it generally is considered to make the effect of vinyl chloride resin degraded.When thermoforming, the Degradation of allylic chlorine atom and association produces in whole resin material everywhere, thus not unexpected, in order to offset this Degradation, stablizer is distributed in the whole material, to stop increasing of allylic chlorine atom in each chain.Understood fully above-mentioned mechanism, people just seek the more efficiently stablizer that can stop allylic chlorine atom to increase fast, and lower processing temperature.

Consider known glass fibre enhanced ryuron when temperature improves owing to increasing of allylic chlorine atom be easy to the degraded, more followingly just merit attention especially: now have recognized that, these general undesirable allylic chlorine atoms just, they are absolutely necessary for the reaction that produces a kind of uniqueness between the primary amine groups (being called the reactive amines part) of aminosilane coupling agent and ryuron chain.This reaction makes the intensity of the polymkeric substance of such thermoforming vinylchlorid outside having surprisingly just: this homopolymer is with being to produce the glass fibre that above-mentioned essential reaction passes through special " surface treatment " to strengthen.

Like this, more generally, the invention relates to vinylchlorid and a kind of can with the monomeric multipolymer of its copolymerization, in this multipolymer, vinylchlorid with a kind of under various thermoforming conditions foot can produce the amount of allylic chlorine atom and exist.If in the vinylchlorid chain, there is the segment of 10 or 10 abundant above carbon atoms, then can be with the chlorination of multipolymer secondary, the allylic chlorine atom that is easy to react with generation.Such vinyl chloride copolymer can be secondary chlorating or secondary chlorating not, and ryuron, and system is referred to as " vinyl chloride resin " in this article.

So-called " carbon atom segment " is meant the part of polymer chain, and this chain is the polyvinyl chloride chain on characteristic, and 57% Cl promptly has an appointment in this segment.When the Cl content in the segment increased, as when vinyl chloride copolymer or homopolymer are chlorinated (secondary chlorination), the difficulty that produces active allylic chlorine atom also increased thereupon.These segmental exist and can identify by such composing with nucleus magnetic resonance (NMR) pointed in the following document in polymkeric substance: the United States Patent (USP) 4 of Richard G.Parker, 350,798 and 4,377,459, here, as having done complete description in this article, above-mentioned by reference document is herein incorporated its content.

Term " by surface-treated " or " surface-treated " are meant such glass fibre, no matter its form is tow, rove, fibrous bundle or yarn, they are through special processing, to be exclusively used in the glass fibre of GFR thermoplastic resin.Do not claimed undressed " primary " or " bare " glass fibre by the surface-treated glass fibre yet.For being used for the enhancing of resin, fiberglass surfacing must have " surface treatment agent ", and this treatment agent is coupler or title " coating " and the combining of " membrane-forming agent " in the present invention, and we do not consider that their actual combining form on fiber surface is any.

" coating " or " coupler " generally is to be selected especially according to glass fibre being used for specific resin wherein by the manufacturing firm of fiber.Once adopted many coating, but common employing is organosilane.At United States Patent (USP) 2,563,288,2,563,889,3,318,757,3,493,461 and many other patents in all can find the example of some silane.On the books in other coating people's such as J.T.Iglehart in the 22nd session of reinforced plastics branch of association of Plastics Industry Company the article " toughener to the intensity of glass fibre enhanced thermoplastics and the influence of performance ".

Some has only used the GFR matrix material of the glass fibre that covers with coupler to have the obvious intensity of having improved.Yet thinking provides suitable coupler simply, just can make matrix material after one month, still can keep its original dry strength in immersing water, and this opinion is unsubstantial, and practical situation are not inconsistent with it.

Certainly, the those of skill in the art in present technique field can give one's full attention to, and the selection of coating and membrane-forming agent (between articulamentum) is two variablees that influence in the multiple variable of GFR mechanical strength of resin and performance.Generally also can recognize, even selected coating and membrane-forming agent best for strengthening certain concrete resin, and the length diameter of used glass fibre and glass types have also been determined, the input coating of people and (or) membrane-forming agent also may be very little, perhaps one of them is too many, or the two is all too many.In any case, more following is conspicuous: because the variable that is explored combination has so much selection, so that make not simple widely repetition test (such as the test that those of skill in the art were accustomed to), also may be a kind of least appropriate methods of seeking the optimization variables combination.If can understand fully the basic physical/chemism that may cause finding the optimization variables combination, then this task will be simplified greatly.

According to this provide one preferably the method reasonable approach of making gratifying (if not good) GFRVC resin composite materials study, at United States Patent (USP) 3,493, point out that key variables are selections of organosilane in 461.This article has proposed the hydrolysate series of very big silane and silane to the manufacturing of GFRVC matrix material, as long as can the glass fibre through silane treatment closely be contacted each other with polyvinyl chloride resin in any mode easily, carries out thermoforming then and gets final product.Disclosed a large amount of silane in specification sheets, and be considered in equal or their hydrolysate that is more or less the same of effect, mentioned aminoalkyl tri-alkoxy silicomethane (the 2nd hurdle of (c) group in specification sheets), it comprises the compound of multiple no primary amine active part.Disclosed thumping majority silane, owing to do not produce the necessary primary amine active part of allylic chlorine atom that needs for catalysis, so the generation to allylic chlorine does not have gratifying katalysis, certainly, people can recognize that also the hydrolysate of these silane can not play this effect equally.

Resemble United States Patent (USP) 3,644,271 wait some reference to point out, key is the powdery PVC of designated size and the suitably heating and the kneading process of the mixture of the granular PVC of granularity, and the specified volume of the every kind of PVC that calculates by the weight of used glass fibre; And think that other all variablees are quite accessory.This patent even proposition " obtain the difficulty of good bond, because the appearance of the suitable processing agent of glass fibre is overcome in fact between thermoplastic materials and the glass fibre.”

In a lot of prior art documents, assert that key is the membrane-forming agent that provides suitable, it is vinyl chloride-ethylene base trialkoxy silane multipolymer, and glass fibre is surface-treated or bare, the degree of the additional reinforced effects of articulamentum is not played important decisive action (for example see United States Patent (USP) 3, the 928,684, the 4th hurdle 46～53 row).

Do not have document to recognize, near the zone that allylic chlorine atom can partly react with the primary amine of coupler fiberglass surfacing, have the criticality that produces allylic chlorine atom.Certainly, under extrusion temperature, single also can produce the indefinite allylic chlorine atom of its quantity, but these Cl atoms produce in whole hot resin material, and restrained immediately because there being stablizer by thermal initiation.Therefore, need their zone almost not have what value near the indefinite allylic chlorine atom pairs fiberglass surfacing of the quantity that produces by thermal initiation.To the understanding of this phenomenon, impel us to seek a kind of like this coupler just, it in the near zone, has fabulous katalysis to generating allylic chlorine atom around glass fibre.

Yet, find that once not only the amount of the allylic chlorine atom that is produced by aminosilane is not enough, and the wet tenacity of the GFRVC resin of making thus is so unacceptably low, so that do not have commercial significance.So-called " wet tenacity ", we specifically are meant the intensity that immerses in 50 ℃ of water and keep the GFRVC resin composite materials after at least 900 hours.Therefore, strengthen the katalysis of aminosilane and the wet tenacity of reinforcement GFRVC resin composite materials, the two all is the problem that needs solution.

Clear and definite is that the selection of forming the specific components of surface treatment agent is to obtain the katalysis of needs and the key of wet tenacity.Therefore, these two fundamental components to " surface treatment agent " of forming glass fibre are analyzed discriminating, and provide the heat that needs to produce to promote allylic chlorine atom, simultaneously the feed glass fiber is coated and the amount of membrane-forming agent, like this as the realization of following purpose pointed out by way of: develop a kind of composition, this composition is not conspicuous, but independently develop; Develop a kind of appropriate method that granulation is carried out in this composition injection molding; The various moulded products that exploitation is made with this composition.

Have been found that, solvent-free VC resin is with effective enhancing of glass fibre special owing to having adopted " surface treatment agent ", this treatment agent is combined with the extraordinary membrane-forming agent that contains alkylene oxide by the aminosilane coupling agent with reactive amines part substantially and constitutes, they all have makes the special catalytic performance that produces allylic chlorine atom in the VC resin chain, can not only improve the dry strength of GFRVC resin composite materials, also improve its wet tenacity especially.

So general objects of the present invention provides a kind of glass fibre enhanced (GFR) VC resin, wherein glass fibre is to use the surface treatment agent of being made up of following two compositions to handle: the aminosilane coupling agent that the reactive amines part (ⅰ) is arranged, can obtain a kind of compound behind it and the resin reaction, there is a peak at the 5.65ppm place in its proton resonance spectrum; (ⅱ) membrane-forming agent of being made up of polymkeric substance basically, this polymkeric substance to be having about 2 rudimentary open loop alkylene oxides to about 4 carbon atoms as the element in the repeating unit, but wherein can contain or not contain the part of another copolymerization.This resin is stable by the common stablizer that is used for thermoset resin.

Specific purpose of the present invention provides a kind of GFRVC resin, and it is by organic metal salt or soap or has the organometallic compound of carbon-to-metal bond stable that glass fibre wherein carried out surface treatment with aminosilane coupling agent and membrane-forming agent.Coupler is represented by following molecular formula:

H ₂NR ¹-（R ¹NH） _n-Si（R ²O） ₃

In the formula, R ¹Representative has the alkylidene group of 2 to 5 carbon atoms, and n represents an integer with 0 to 3,

R ²Representative has 1 alkyl to about 6 carbon atoms.

Membrane-forming agent is represented by following molecular formula:

R ³O

（R ¹O） _m-（X） _n′

_m′-R ⁴

In the formula, X is monomeric group, and this monomer is selected from Epicholorohydrin, tetrahydrofuran (THF), β-propine lactone, styrene oxide, maleic anhydride and 1 aliphatic dialcohol to about 12 carbon atoms;

R ³And R ⁴All can represent respectively be selected from by hydrogen and 3 to a group forming of the alkyl of 30 carbon atoms in a member;

N ' is an integer of 0 to about 100;

M is the mean number of repeating unit, and its value arrives in about 200,000 the scope 5;

M ' is the mean number of repeating unit, its value from 1 in about 5000 scope;

N ' is less than m;

And, R ¹Occur with relative uneven order with X.

Another specific purpose of the present invention provides a kind of by the stable GFRVC homopolymer of organometallic stabilizer, wherein the length of used glass fibre is less than 1mm, they are to be that 0.1～about 1%(is by weight of glass with weight percent) the hydrogen base silane with active primary amine part, with weight percent about 0.1% to about 1%(in weight of glass) the water-soluble film forming agent that contains the alkylene oxide repeating unit carry out surface treatment, therefore in the GFRVC homopolymer after thermoforming, the combination of glass fibre and homopolymer is so firm, so that the matrix material of thermoforming can be owing to cohesive failure damages.So-called " cohesive failure " is meant the GFRVC resin sample because the destruction that the tearing of resin and interlaminar resin causes, rather than because the destruction that the tearing between glass surface and the resin (" adhering to destruction ") causes.Therefore, cohesive failure is the characteristic by resin, rather than determine by the connection between resin and the glass.

The present invention also has a specific purpose, but just provides the homopolymer pellets material that aforesaid pattern of fever is the GFRVC of formed article, and the characteristics of this material are to have good dry strength, and immerses in 50 ℃ of water and still have good wet tenacity after 900 hours; It can be because of interior poly-destruction; And its tension wet tenacity approximates or is better than the dry strength of the same compound material of film former-free.

Other specific purpose of the present invention relates to: the GFRVC resin is the granulation process of VC homopolymer particularly; The thermoforming of particulate material, particularly injection molding; The thermoforming matrix material of making by the GFRVC resin; By carry out the formed article of pulling out that continuous glass fibre that special surface handles or felt material make by regulation technology of the present invention; These all will be described in detail hereinafter.

Above-mentioned and some other purpose and its advantage of the present invention; clearer and more definite by following description meeting; the relevant Photomicrograph in conjunction with the preferred specific embodiments of the present invention is carried out in description, so that compare, and witnesses for the claimed feature of the present invention.

Fig. 1 is that 1200 of GFRPVC matrix material cross section shows little enlarged photograph, and the glass fibre in this matrix material is only handled with silane coupling agent, does not use membrane-forming agent, and this cross section is the test specimen rupture cross section that dumb-bell shape stretches and causes.

Fig. 2 is that 1200 of GFRPVC matrix material cross section shows little enlarged photograph, and the glass fibre in this matrix material is handled with aminosilane coupling agent and vinyl acetate (PVA) membrane-forming agent, and this cross section is the rupture cross section that the dumb-bell shape tensile test specimen causes.

Fig. 3 is that 1200 of GFRPVC matrix material cross section shows little enlarged photograph, and the glass fibre in this matrix material is handled with aminosilane coupling agent and polyether glycol membrane-forming agent, and this cross section is the rupture cross section that the dumb-bell shape tensile test specimen causes.

Fig. 4 is Geo

The trace figure of proton resonance (pmr) spectrum of the thermoforming GFRPVC matrix material of 110 * 346PVC.Glass fibre in this matrix material is handled with the aminosilane with active primary amine part.

Fig. 5 is the Geon that pulverizes through traditional method ^*110 * 346 PVC are with the pmr spectrum trace figure that is similar to the method gained that obtains Fig. 4, wherein without any aminosilane-treated.

When producing glass fiber bundle, a large amount of glass fibre is pulled out at a high speed from the glass melting screw tap, and this screw tap is located on the top of a little spout of telescopic in the frit smelting furnace.When these fibers are drawn out, before being integrated sub-thread or multiply, it is handled with aquifer surface treatment agent.This surface treatment

* " Geon " is the registered trademark of B.F.Goodrich company.

Agent must be avoided wearing and tearing mutually between filament by the protective glass fiber, and makes glass fibre and want the enhanced material compatible.For reaching this purpose, aquifer surface treatment agent is mainly by firm and machinable membrane-forming agent of fibrous bundle and coupler are formed.Usually add lubricant and static inhibitor,, can also add auxiliary sometimes, but the selection of auxiliary not a content of the present invention for preparing the fibrous bundle of final application.

The form of surface-treated glass fibre that is used for strengthening polymkeric substance is based on continuously and short sub-thread or multiply fabric and the rove of cutting (one group of multiply).Short glass fiber bundle of cutting and the short fibre glass roving of cutting are mainly used to make the block molding mass of sheet molding compound and the thick product molding mass of GFR polymkeric substance.Surface treated glass (fiber) generally is to be sold according to the specific end use that will use it for certain particular polymers by its manufacturers, and surface treatment agent is to select at specific polymkeric substance.Strengthen the VC resin but be exclusively used in, surface-treated glass fibre does not also have ready-made at present.

What preferentially select for use is the fiberglass filament made from the boron sikicate aluminum lime glass that does not contain yellow soda ash relatively, preferably selects " E " and " S " glass for use.Yet some other glass also can adopt, low carbon acid soda glass for example, (as " C " glass).Can not reach suitable strength when once finding to adopt the high carbon acid soda glass.Filaments of glass is made by already known processes, and its diameter is less than 20 microns, although with about 10 to about 16 microns be-kind of glass and all not really strictnesses in practice of the present invention of the diameter of filament.

The length of filaments of glass and they are become fiber by intoxicated drum, still these fibers are integrated yarn, rope or rove again, or be made into felt material or the like, neither be very important to the present invention, yet, when preparation composition of the present invention, be to utilize such filament glass easily: it is that the about 1mm of length is to about 27mm, to cut strand less than 5mm for good weak point.Be used for the composition (these particulate material are used to make molded and shaped article, its equivalent diameter at about 3mm in the 8mm scope) of production particulate material at optimum, can find shorter glass fibre, its length is generally less than 1mm.This is because in stirring the process of closing, and considerable fracture can take place, so that some fiber can be short to 100 microns.

When the weight percent of glass fibre about 5% in about 50% scope the time (by the gross weight of glass fibre and resin), the thermoforming performance of composites is best, wherein the length of institute's fibre-bearing about 500 microns in about 1mm scope.When content of glass fiber in the matrix material less than 5% the time, we estimate having little significance of commerce that it strengthens benefit; When glass fibre weight surpassed the weight of VC resin, the compound that obtains did not possess gratifying processing characteristics.

Glass fibre should be with (ⅰ) about 0.1% to about 10% weight (original weight that is per 100 parts of glass fibre be with 0.1 to 1 part of weight), the aminosilane of the formula I of 0.2 to 0.6% weight preferably, and (ⅱ) about 0.1 to about 1% weight, preferably 0.2 membrane-forming agent to the formula II of about 0.6% weight coats.Because the length of glass fibre is less in the composition, thus the intensity increase of enhanced thermoforming matrix material be decided by to cover the amount of the surface treatment agent on the fiber-as long as this measure in the scope that provides in the above.

Can be used for PVC of the present invention is ryuron, and it is the porosu solid coarse grain that obtains with body or suspension polymerization, and the coarse-grained mean diameter of PVC that is transformed into CPVC generally surpasses 20 microns, and most of particulate diameter is above 50 microns.The configuration of surface of PVC and CPVC, especially its porosity and (ratio) surface-area are the key properties of decision polymer physics performance.Because CPVC generally is also referred to as " secondary chlorination " by chlorination PVC() obtain, found that the performance of CPVC product can be adjusted by the polymerizing condition of accurate control raw material PVC in a big way.The production method of CPVC is at United States Patent (USP) 2,996, and 489,3,506,637,3,534,103 and 4,412, disclose in 898,, carried out complete description as herein here, above-mentioned by reference each piece open source literature wherein related content is herein incorporated.

Preferably the PVC with suspension polymerization is used as raw material, and its porosity is about 0.22 to about 0.35cm ³In/g the scope; Its specific surface is about 0.6 to about 3m ²In/g the scope; Its limiting viscosity arrives in about 1.2 scopes about 0.53, that is to say that it has than higher molecular weight.The molecular weight of PVC is relevant with its limiting viscosity, can be by United States Patent (USP) 4,412, and method described in 898 is measured.The limiting viscosity of the most frequently used polyvinyl chloride resin is about 0.53 in about 1.1 scopes or higher slightly, and it is called as " hard PVC ".

That best is the commodity Geon of B.F.Goodrich company ^R110 * 346PVC, Geon ^R623 and the 625CPVC resin.

Aminosilane generally is a liquid, because the amount that need be deposited on the glass fibre is smaller, so be that unhydrolysed aminosilane is coated on the fiber with solution (the normally aqueous solution) form, the concentration of this solution is previously selected.The concrete coating method of aminosilane be conventional, be generally the known method of the public, in the prior art, for example at United States Patent (USP) 4,410,645 and 4,254,010 and the document wherein quoted in existing the description.Here, as having done complete description in this article, these documents by reference, wherein related content is herein incorporated.

Aminosilane coupling agent with aforementioned formula I is the commercially available prod that is specifically designed to surface-treated glass fiber.Some are when being used in combination with the membrane-forming agent of aforementioned formula II, and the aminosilane that can be effectively used to produce GFRVC rosin products of the present invention is as follows:

β-aminomethyl trimethoxy silicomethane,

N-β-aminoethyl-

-aminopropyl trimethoxy silicomethane

N-β-aminoethyl- -aminopropyl-triethoxy silicomethane

-aminopropyl trimethoxy silicomethane

-methylamino-propyl trimethoxy silicomethane

-ethylamino propyl trimethoxy silicomethane

-aminopropyl-triethoxy silicomethane

-aminopropyl tripropoxy-sil(ic)ane

-aminopropyl methyl diethoxy silicomethane

-aminopropyl ethyl diethoxy silicomethane

-aminopropyl diethylamino phenyl oxygen base silicomethane

-aminopropyl isobutyl-dimethoxy silicomethane

The N-(2-aminoethyl)-N '-[the 3(triethoxy is silica-based) propyl group]-1

The N-(2-aminoethyl)-N '-[the 3(trimethoxy is silica-based) propyl group]-1

δ-aminoisobutyric base triethoxy-silicane

δ-aminoisobutyric ylmethyl diethoxy silicomethane and

β-aminoethyl triethoxy first silicon

Though it is that effectively suitable membrane-forming agent is that end group is the polyethers of OH that the multipolymer of molecule formula II is used as membrane-forming agent, the alkylene oxide in its chain is the rudimentary alkylene oxide of open loop, is typically oxyethane, propylene oxide or butylene oxide ring.

Chain can be made of the residue of single alkylene oxide unit, or the copolymerization structure of different alkylene oxide unit residues.

The mean number of repeating unit " m " is more preferably in about scope of 100 to 10,000 in about 5 to 200,000 scopes.Because surface treatment agent is coated on the glass fibre with the solution form, membrane-forming agent preferably can be dissolved in common organic solvent (solvent is soluble), and can be water-soluble ideal with used polyethers membrane-forming agent, so just can use the aqueous solution of 2～30% concentration that glass fibre is carried out surface treatment with common method.

Radicals R ³Can be in the some kinds of alkyl any one, these alkyl comprise phenyl, substituted-phenyl and various fatty acid-based such as the alkyl that is generally used for the polyether-type membrane-forming agent.If desired, polyethers can be with being a kind of multipolymer, but the i.e. multipolymer of alkylene oxide and another copolymerization component (for example polyvalent alcohol, particularly lower aliphatic glycol, as propylene glycol), and this multipolymer can keep ideal membrane-forming agent characteristic; And as long as the number of open loop alkylene oxide unit is preponderated in its chain, this membrane-forming agent just can provide promotion to produce the desirable katalysis of allylic chlorine atom near glass surface.Multipolymer (II) generally is a kind of irregular multipolymer, and it can contain the segment of every kind of repeating unit, but the group of every kind of comonomer is connected to the order particularly important not on the chain.Multipolymer (II) is the multipolymers of those n ' less than 0.5m preferably.

The alkylene oxide membrane-forming agent of preferentially selecting for use is represented by following molecular formula:

R ³

（R ¹O） _m R ⁴

The meaning of symbol is with aforementioned in the formula, and the number of m arrives in about 10,000 the scope about 100.

Some more preferred membrane-forming agent polymkeric substance are as follows: polyethylene oxide, water-soluble poly propylene glycol, polyoxyethylene list oil ether, polyoxyethylene single-stearic acyl ether, polyoxyethylene monododecyl ether, polyoxyethylene list nonyl benzene ether, polyoxyethylene two hard ester acyl ethers, polyoxyethylene dinonyl phenylate etc.

In preferred forms of the present invention, the GFRVC thermoplas tic resin composite is made up of to the glass fibre of about 35% weight the VC resin and 10 of 100 parts of weight substantially, and this glass fibre is coated with the 0.2% specified amount membrane-forming agent to about 0.6% weight.If the amount of above-mentioned each composition obviously exceeds the scope of stipulating above, then the plasticity-of glass fibre and resin and processing characteristics are with variation, and dry strength and wet tenacity also all can reduce.

Term used herein " substantially by ... form " meaning promptly: those compositions of naming are major ingredient, although can comprise that also other does not destroy the composition of benefit of the present invention.Such composition can comprise the common additives that resembles weighting agent (as talcum, mica, clay etc.), photostabilizer, thermo-stabilizer, oxidation inhibitor, pigment and the dyestuff, and these additives add for specific purposes.Have recognized that the amount of additive therefor is influential to the physicals of thermoforming matrix material.

The test preparation of matrix material

Cut the glass strand bundle except that short, all furnish components all in the Henschel high-speed mixer, in " powder mixes " 30 seconds under 3000 rev/mins of rotating speeds, refine every kind of powdered mixture then at Getty type 604 " * 9 " electromotive roller refining machine top roll, 215 ℃ of roller refining temperature, roll gap about 0.025 ".Then with 105 gram powder feeding roller refining machines, be melted through one minute, after this, the short glass fibers that restrain the about 6.4mm of length through 44 of aminosilane and membrane-forming agent processing are being added in the VC homopolymer under the roller refining continuously, take out the GFR sheet material from roller refining machine, do mark, to distinguish roller refining direction and transverse direction.

The sheet stock that roller is become is molded as has 6 " * 6 " * 0.025 " thin plates of constant volume.In this process, make mould 199 ℃ of preheatings 10 minutes.Then 65 gram GFRVC thin plates are added in the mould.Attention: guarantee to make all to be added to the blank maintenance equidirectional that the roller in the mould is smelt.Then mould is put in the press, in one minute timed interval, carries out the pressurization of 5,10,20 and 30,000 ft lbfs and unload press operation.Then pressure is raised to 30,000 ft lbfs for the second time, and kept 1.5 minutes.Then mould is transferred in the chilling press, let alone add depress the cooling 5 minutes.Cut from these plates and to dig out the dumb-bell shape tensile test specimen.Note also, prepare these tensile test specimens the time, make sample direction with roller refining direction unanimity.

By the data of following table I as seen, PVC matrix material (1# matrix material sample with bare glass enhanced stabilization, original pattern) wet tensile is bigger slightly than half of its dry tensile strength, and wet tenacity was measured later in immersing 50 ℃ of water in 900 hours.And the 2# sample is with the glass preparation of film former-free, but does not contain the active primary amine part in the used silane coupling agent when handling this glass, and its performance is not relatively obviously improved with bare glass (1# sample).When glass only uses aminosilane coupling agent (I) to handle (3# sample), properties of sample improves significantly, and almost high by 50% than the intensity of original pattern, wet tenacity also obtains the improvement of certain degree, but this improvement does not have any commercial significance, because particularly wet tenacity is low as to make us being difficult to accepting.

The same stabilization resin composite materials (4# sample) of glass fibre enhanced with aminosilane coupling agent (I) and the processing of polyvinyl acetate base ester (PVA) membrane-forming agent, its intensity and 3# sample (glass is handled through aminosilane (I), does not use membrane-forming agent) are roughly the same or smaller slightly.Have only wherein glass both to use aminosilane (I), use sample that polyethylene oxide (PEO) membrane-forming agent (II) handled and original pattern again relatively, its wet tenacity increases and is twice, and dry strength almost increases and is twice.It should be noted that most that the wet tensile of 5# sample approximates the dry tensile strength of 3# sample.

In the table I, all matrix materials all are to prepare with identical method, wherein adopt the Geon of 100 parts of weight

The two different hot sulfenyl glycolic acid dibutyl Ya Xiji ester stabilizers of hot surface treatment agent (Thermolite) 31-of the glass of 110 * 346PVC, 44 parts of weight and 3 parts of weight.In the data rows table I below.

The table I

PVC matrix material dry strength * wet tenacity *

(pound/inch ²) (pound/inch ²)

1# glass fibre-bare (original pattern) 10,400 6,000

2# glass fibre W/ glycidoxypropyl 10,900 7,000

(glycidoxy) propyl group silicomethane ¹

3# glass fibre W/ aminosilane ², film former-free 13,300 10,500

4# glass W/ aminosilane ²+ PVA membrane-forming agent 13,300 6,000

5# glass W/ aminosilane ²+ PEO membrane-forming agent 18,400 13,400

* adopt the Instron trier at room temperature to measure

1

-glycidoxypropyl trimethoxy silicomethane

2N-β-aminoethyl-

-aminopropyl trimethoxy silicomethane

In order to measure wet tenacity, tensile bar is dipped in 50 ℃ the water bath with thermostatic control taking-up in pre-specified time.Make its surface drying with each strip of paper handkerchief wiping, on the Instron trier, test then.All samples is all tried in 1 hour after taking out from the pond.

It all is in room temperature and 0.2 that all tensile strength are measured "/minute sample holder spacing rate under carry out.

The fracture surface of tensile bar is checked by scanning electronic microscope (SEM).The element scintigram of oxygen and silicon is to go up the energy dispersive X ray ability (compacity) that is equipped with by SEM to finish, and this is well-known method, and more detailed the introduction seen " Kirk ﹠amp; Othmer, Supra, Vol.2, Pg 634 ".

Being used for measuring the fiber sample of staple length, is the plate that roller is smelt and is pressed into, and uses the THF(tetrahydrofuran (THF)) dissolve and obtain behind the PVC.Residual glass fibre is collected on the filter paper, is placed in the retort furnace to carry out thermal purification at 600 ℃, measures at last.

Fig. 1 is the electron scanning micrograph of tensile bar rupture cross section under 1200 times of amplifications of 2# matrix material, and in the close zone of glass fibre fracture place, glass fibre is clearly.As if fiber be connected in fiber head well and stretch out on the polymeric matrix at place.So-called " clearly " is meant on the fiber and therefore shows that adhesion destroys without any coverture (polymkeric substance).

Fig. 2 is the Photomicrograph of 4# matrix material.Here, the PVA coverture is arranged on the glass fibre, this coverture has hindered the carrying out of coupling process, produces needed tensile strength because it stops PVC to contact with aminosilane and improves.Gap between fiber and the matrix is obvious visible, and fiber passes from the gap and extends out.This strength of materials is low during generally than film former-free, this is considered to " mixed type " behavior and causes in matrix material average interface intensity to reduce causing, and the wet tenacity of Jiang Diing then is that a big chunk of fiber is surperficial owing to the PVA that remains on the fibre-matrix interface has kept hygroscopic cause greatly.

Fig. 3 is the Photomicrograph of 5# matrix material under 1200 times of same amplifications, is coated with one deck PVC polymkeric substance here on Duan Lie the glass fibre, and this shows that combine closely (because of stretching) destroys.This coverture is PVC, and this is to be determined by analysis hereinafter described.In addition, it seems that fiber sticks on the matrix securely, there is not tangible gap to exist between fiber and matrix because observe in the place that fiber passes matrix, the superior strength of this matrix material, no matter be wet tenacity, still dry strength is considered to be present in by hypothesis that covalent linkage between the VC chain of the active primary amine part of aminosilane and polymkeric substance causes.

Fig. 4 is the main relative section that (pmr) figure is composed in the proton resonance of the PVC sample of thermoforming, and this sample is handled with aminosilane (I), but membrane-forming agent useless, this is to read spectrum in order to simplify.This spectrogram is obtained by usual way, wherein adopted the technology that more complete description is arranged: Makromol.Chem.178 in following document, Roger Petiaud and Quand-ThoThan " Branching and Unsaturated Structures and Radically Polymerized Poly(Vinyl chlorides) Studied by High Resolution Proton Magnetic Resonance " here 177(1977), as having done complete description in this article, above-mentioned by reference document is herein incorporated this technology.In 5.15ppm(δ scale) peak located provides the evidence that responds and exist between the allylic chlorine atom in the amino of aminosilane (I) and VC chain.(next and the primary amino silane reaction) PVC that refining forms for roller, this peak generally moves on to the 5.85ppm place, and still in spectrum, there are two keys in its part in this explanation PVC chain.

Fig. 5 be this PVC of PVC(of conventional roller refining and being used for when making its pmr spectrum for the matrix material of Fig. 4 used PVC identical) pmr compose, this PVC has been heated to temperature of fusion, be higher than 160 ℃ but be lower than about 200 ℃.This pmr spectrum is to obtain the used method of Fig. 4 and obtain with being similar to, and with preceding the same, has only got wherein main and comparable part.Peak at the 5.85ppm place is clearly visible.In addition, general distinctive bimodal (its mid point is at the 4.05ppm place) that in roller pmr spectrum refining, (with aminosilane) unreacted PVC, is occurred, disappeared after GFRVC matrix material of the present invention forms, in this matrix material, aminosilane has reacted.This pmr spectrum and the bimodal existence of this feature of common PVC, the existing description in " Die Ange-wandte Makromo-lekulare Chemic 83(1979) 183-196(Nr.1318) ".

Can recognize by the elemental map of ruined matrix material whether the coverture on the fiber ends of exposing is polymkeric substance from the fracture sample.The chlorine elemental map is drawn under 3000 times of amplifications, and element silicon figure draws under 1500 times of amplifications, and element silicon figure shows that 5# is rich chlorine, and in the SEM Photomicrograph in the obvious visible of the polymeric cover zone, cl concn is the highest.Because not chloride in the primary membrane-forming agent, so the existence of this explanation chlorine is because the evidence that the PVC key is linked on the fiber was both clear, convincing again.

The other analysis can confirm the above-mentioned reaction of allylic chlorine atom.For example, in the raman spectrum wave number at 1500cm ^-1And 1530cm ^-1Between the relative intensity at peak show, the PVC that handles with the aminosilane coupling agent that the active primary amine part is arranged, when thermoforming, with same but do not have the PVC of aminosilane to compare, the conjugation unsaturation is less.This is the evidence of allylic chlorine atomic reaction in the chain, and people can anticipate the result that this conjugation unsaturation reduces by this reaction.

The preparation of particulate material:

With Geon ^RIn 110 * 346PVC and the other batching composition feeding Buss kneader, after material was mediated therein, the most handy blank forcing machine carried out pelletizing to composition.These compositions with premix several minutes in the Henschel mixing tank for well, this be for obtain all can flowable powder material.Before the feeder that infeeds the Buss kneader, these powder are poured into ribbon or stirrer preservation and stirring.

Have the Buss kneader of two heating zone to be used as the 7L/D(slenderness ratio) the batching extrusion machine.Utilize the 1.2 ET46 loaders of adjusting the position that powder mixture is added to first hole.From from the downward feed port of first hole 4L/D distance, adding the short glass fiber that is shorter than 2.5cm.Glass fibre and powdered mixture are rubbed and mixed are discharged to then in the pelletizing forcing machine through 3L/D length, and this forcing machine has the heating zone of oneself.

The pelletizing forcing machine is a low compression 6L/D pump forcing machine, it is furnished with the share split mould of a band hot side cutting knife, the resin that contains glass fibre is exposed under 16 ℃ of temperature in about 18 ℃ of scopes before extruding from the share split mould momently, be cut into homogeneous granules then, particle is sent to separator-receptor and by air cooling.GFRPVC is before just extruding from the share split mould, and its temperature can reach about 205 ℃.After fines is blown into vacuum recovery system, with cooled particle pack.

The extrusion moulding of GFRPVC particulate material:

Particulate material with aforesaid method production is extruded it under the 25L/D working order with the 25mmHaake formula single screw extrusion machine that has one 2/1 compression screw rod usually.This forcing machine moves under about 20 rev/mins of rotating speed, the condition of extrusion pressure in about 1500～2000 pounds of/inch scopes.Under 25: 1 working ordeies, five temperature-controlled areas are arranged in the cylindrical shell, a temperature control district is arranged on the die head.Barrel temperature district temperature fix on from 150 ℃ in about 170 ℃ scope, the temperature in die head temperature district fixes on 175 ℃.

Used special die head is one 0.125 " * 1.0 " sealing film head, and the extrudate that comes out from forcing machine is sent to travelling belt.

The GFRPVC rod pull out moulding:

The axially extended parallel compound yarn that makes the glass roving of handling through aforementioned surfaces enters in the right angle feed die separately by each aperture, and the PVC of fusing is pressed into this die head with the dipping rove.Then the rove strand behind the dipping is introduced in the die head, there unnecessary resin is removed, and strand is closely combined by the shape of required rod, it is cooled off gradually.

The making sheet of GFRPVC sheet stock:

The GFRPVC sheet stock is preparation like this: with the glass fibre of PVC dipping through the aforementioned surfaces processing, and make PVC and the weight of glass fibre in every thin slice about equally.Some such thin slices are cut into predetermined pattern, in mould, gather into folds, then with ordinary method 160～200 ℃ of temperature, about 1000 pounds/inch of pressure ²Under the condition of (about 30,000 ft lbfs) it is molded as the setting article.

With being similar to previously described each method, CPVC(with particulate material or fusing floods with aminosilane of the present invention and the surface-treated glass fibre of film former with it) be raw material, can prepare the GFRCPVC matrix material, and can repeat and both reached good dry strength reliably, also reach good wet tenacity.

Claims

1, a kind of vinyl chloride resin of thermoforming and thermoplastic compounds of glass fibre of being particularly suitable for, it contains the mixture of following composition:

(a) vinyl chloride resin of about 50～95% weight (by the gross weight of glass fibre and vinyl chloride resin), wherein the vinylchlorid of each repeating unit partly contains from about 57% chlorine to about 72% weight;

(b) from the diameter of about 5% to 50% weight less than about 20 microns glass fibre, this glass fibre is coated with the surface treatment agent of being made up of following composition basically:

(i) aminosilane coupling agent of reactive amines part is arranged, it with said resin reaction after, obtain its proton resonance compose in the 5.65ppm place have a peak a kind of compound and

The (ii) membrane-forming agent that mainly constitutes, this polymkeric substance by a kind of polymkeric substance have contain from about 2 to the rudimentary open loop desaturation oxygen of about 4 carbon atoms as the basal component the repeating unit, but wherein can also contain or not contain the component of another kind copolymerization; With

(c) be used for the stablizer of said homopolymer, its consumption is enough to make said composition to have desired stability when thermoforming.

2, composition as claimed in claim 1, said composition is particularly suitable for directly infeeding injection moulding machine, by glass fibre and vinyl chloride resin gross weight, the amount of said vinyl chloride resin arrives in about 95% the scope 50%, the amount of glass fibre arrives in about 50% scope about 5%, and Fibre diameter arrives in about 16 micrometer ranges at about 10 microns.

3, composition as claimed in claim 2, wherein said aminosilane coupling agent is expressed from the next:

H ₂NR ¹-（R ¹NH） _n-Si（R ²O） ₃

R in the formula ¹Representative has 2 alkylidene groups to about 5 carbon atoms, and n represents an integer of 0 to 3, and R ²Representative has 1 alkyl to about 6 carbon atoms; Said membrane-forming agent is the solvent polymer soluble, can be expressed from the next:

In the formula, X is a residues of monomers, and this monomer is selected from Epicholorohydrin, tetrahydrofuran (THF), β-propine lactone, styrene oxide, maleic anhydride and has the 1 ester aliphatic diol to about 12 carbon atoms, R ³And R ⁴Can represent hydrogen atom respectively or have the alkyl of 3 to 30 carbon atoms, n ' is an integer in 0 to 100 scope, and m is the mean number of repeating unit, its value arrives in about 200,000 the scope 5, and m is the mean number of repeating unit, its value is 1 in about 5000 scopes, and n ' is less than m, R ¹Occur with relative inhomogeneous order with X.

4, composition as claimed in claim 3, wherein said membrane-forming agent is a water-soluble polymers, can be expressed from the next:

R ³O-（R ¹O） _m-R ⁴

R in the formula ¹Expression-CH ₂-CH ₂-.

5, composition as claimed in claim 3, wherein said aminosilane be selected from β-aminomethyl trimethoxy silicomethane,

-aminopropyl trimethoxy silicomethane,

-methylamino-propyl trimethoxy silicomethane, -ethylamino propyl trimethoxy silicomethane,

-aminopropyl-triethoxy silicomethane,

-aminopropyl tripropoxy-sil(ic)ane, -aminopropyl methyl diethoxy silicomethane,

-aminopropyl ethyl diethoxy silicomethane, N-β-aminoethyl-

-aminopropyl trimethoxy silicomethane, N-β-aminoethyl-

-aminopropyl-triethoxy silicomethane,

-aminopropyl diethylamino phenyl oxygen base silicomethane, -methyl-isobutyl trimethoxy silicomethane, N-(2-aminoethyl)-N '-[the 3-(triethoxy is silica-based) propyl group]-1,2-quadrol, N-(2-aminoethyl)-N '-[the 3-(trimethoxy is silica-based) propyl group]-1, δ-amino butyl triethoxy-silicane, δ-amino butyl methyl diethoxy silicomethane and β-aminoethyl triethoxy-silicane.

Said membrane-forming agent is selected from polyethylene oxide, water-soluble poly propylene glycol, polyoxyethylene list oleyl ether, polyoxyethylene single-stearic acyl ether, polyoxyethylene monododecyl ether, polyoxyethylene list nonyl benzene ether, polyoxyethylene two hard ester acyl ether and polyoxyethylene dinonyl phenylates.

6, composition as claimed in claim 3, wherein said vinyl chloride resin is the ryuron that contains the chlorine of about 57% weight, or contains from about 58% chlorinated polyvinyl chloride to the chlorine of about 72% weight.

7, composition as claimed in claim 6,, wherein the amount of said aminosilane is in the scope of 0.2% to 0.6% weight (based on the bare glass fibre of 100 parts of weight), and the amount of said membrane-forming agent is in the scope of 0.2% to 0.6% weight.

8, composition as claimed in claim 7, wherein the limiting viscosity of said polyvinyl chloride arrives in about 1.1 scopes about 0.53.

9, for the improvement of the method for granulating of ryuron and glass fibre, comprising:

(a) the said homopolymer (wherein the vinylchlorid of each repeating unit partly contains 57% chlorine to about 72% weight of having an appointment) that contains stablizer is heated to above about 160 ℃ of temperature, but is lower than the degradation temperature of this resin.

(b) will this warmed-up homopolymer and mediate from about 5% glass fibre (based on the weight of glass and homopolymer) to about 50% weight, form a homogeneous material, the diameter of every fiber is less than about 20 microns, this glass fibre covers with surface treatment agent, and surface treatment agent is made up of following composition substantially:

(ⅰ) have the aminosilane coupling agent of reactive amines part, it and this resin reaction obtain in its proton resonance is composed 5.65ppm place have a peak compound and

(ⅱ) basically by having the membrane-forming agent of forming as the polymkeric substance of the basal component in the repeating unit with the rudimentary alkylene oxide of open loop of about 2 to 4 carbon atoms, but wherein can also contain or not contain the component of another kind copolymerization, and

(c) broken this material forms equivalent diameter and is the particulate material of about 3mm to about 8mm.

10, strengthen in order to glass fibre and contain the moulded products that vinyl chloride resin (wherein the vinylchlorid of each repeating unit partly contains from about 57% chlorine to the about 72% weight) matrix material of stablizer is made, in this matrix material, the amount of said resin is to about 95% weight (by the gross weight of glass fibre the matrix material and resin) from about 50%, the amount of glass fibre is from about 5% to 50% weight, its diameter is less than about 20 microns, and its surface coverage is by a kind of surface treatment agent of being made up of following composition substantially:

(ⅰ) have the aminosilane coupling agent of reactive amines part, it with said resin reaction after, obtain a kind of in its proton resonance is composed the 5.65ppm place have a peak compound and

(ⅱ) a kind of membrane-forming agent that substantially constitutes, this polymkeric substance by a kind of polymkeric substance have contain from about 2 to the rudimentary alkylene oxide of the open loop of about 4 carbon atoms as the basal component the repeating unit, but wherein can also contain or not contain the component of another kind copolymerization.

Thereby the tensile strength of this matrix material is at least two times of homopolymer of no above-mentioned glass fibre.