CN1069679C - Thermoplastic rubber-type water-proof coiled material - Google Patents

Abstract

The present invention provides a thermoplastic rubber-type waterproof coiled material which is a rubber-type waterproof coiled material using a thermoplastic elastic body as a base body. Ethene-octene copolymer is adopted as base-body rubber; the components of the ethene-octene copolymer comprise 100 portions of ethene-octene copolymer, 8.8 to 223 portions of filled reinforcing agent, 1.7 to 100 portions of softened plasticizer and 0.5 to 4 portions of anti-aging agent according to weight portions, and 5 to 7.5 portions of activator and 0.05 to 0.7 portions of cross-linking agent can also be added. A vulcanization machining process step is not needed for producing the rubber-type waterproof coiled material, leftover bits and pieces of industrial material, waste material and used products during the production process can be recovered and utilized, and heat adhesion can be adopted for joint seams of construction; the anti-aging performance of the thermoplastic rubber-type waterproof coiled material can reach or exceed the anti-aging performance of the rubber waterproof coiled material prepared by ethylene propylene terpolymer rubber.

Description

A thermoplastic rubber waterproof membrane

The invention relates to a building waterproof coiled material, which is a rubber-type waterproof coiled material based on a thermoplastic elastomer ethylene-octene copolymer.

Rubber-type waterproof membrane is a new type of waterproof membrane developed with the development of synthetic rubber. Compared with traditional asphalt-type waterproof membrane, rubber-type waterproof membrane has light weight, high strength, good elongation, It has the advantages of good tear resistance and aging resistance, strong temperature adaptability, long service life and less construction pollution. The rubber-type waterproof membrane is processed and manufactured with rubber as the matrix and filled with modifiers according to the processing procedures of conventional rubber products. The processing process includes raw rubber plasticating, rubber compound mixing, processing into sheets, vulcanization and other processes. The basic properties that the rubber-type waterproof membrane should have are: resistance to infiltration and penetration of water; low hygroscopicity; stability to temperature changes; certain physical and mechanical properties; corrosion to weather, acid, alkali and microorganisms It has good resistance and resistance; it has good bonding performance and so on. The types of base rubber used in rubber-type waterproofing membranes include neoprene, butyl rubber, EPDM rubber, polyurethane rubber, chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, and combinations thereof. Neoprene is the earliest rubber used in waterproof membranes. It has excellent performance in aging resistance, chemical corrosion resistance, flame retardancy, and oil resistance, but its temperature adaptability is poor. It will continue to cross-link at high temperatures, and crystallize at low temperatures. And the glass transition temperature is higher and hardens, and the processing performance is not ideal. Although it is one of the main varieties of rubber-type waterproof membranes, it has a tendency to be replaced by other rubber-type waterproof membranes. Butyl rubber waterproof membrane has good aging resistance and excellent air permeability resistance due to the high saturation of butyl rubber. Its price is high, its processing performance is not good, and special adhesives must be used to bond it. Due to these defects it was gradually replaced by EPDM waterproof membranes. The polymer structure of EPDM rubber determines that it has better aging resistance, better high and low temperature performance, excellent resistance to acid, alkali and water vapor than the above two rubber waterproof membranes, and excellent processing performance. Also ideal. It has developed rapidly as a high-grade rubber-type waterproof membrane, because its price is relatively expensive, and its wide application is limited. Chinese patent CN1097435A discloses a production method of a styrene-butadiene block copolymer modified asphalt waterproofing membrane. The aging performance and tensile performance are still poor, and its performance cannot be compared with that of EPDM waterproof membrane. Czech patent CS271,374 discloses a waterproof membrane composition, which contains a mixture of neoprene/ethylene propylene rubber blends and polyvinyl chloride resin or vinyl chloride resin, carbon black or inorganic fillers, mineral oil and cross-linked system. Compared with ethylene propylene rubber waterproofing membrane, it has better oil resistance, but this waterproofing membrane still needs vulcanization. The biggest disadvantage of thermosetting rubber is that it must be vulcanized before it can be used. The vulcanization process not only increases the complexity and cost of processing, but also makes it very difficult to recycle and utilize leftovers, waste materials and used products after vulcanization.

Thermoplastic elastomer is a material that combines the advantages of rubber and plastic. Its plastic phase is flowable at high temperature and acts as a physical crosslinking point at room temperature. This physical crosslinking is thermally reversible. Therefore, it can be processed and formed in the same way as thermoplastics, and it has the elasticity of rubber in a wide temperature range. Its processing can save complex and energy-intensive vulcanization process. Considering the aging resistance and cost of raw materials of thermoplastic elastomers, their application in waterproof membranes is greatly limited. Up to now, there have been no reports that thermoplastic elastomers have been successfully used as matrix rubber in waterproof membranes.

The purpose of the present invention is to propose a new type of waterproof roll material with excellent aging resistance and processability. Using ethylene-octene copolymer as the base rubber, supplemented by appropriate filling modification, a waterproof membrane with both performance and cost is obtained.

A kind of thermoplastic rubber type waterproof coiled material provided by the present invention is made up of matrix rubber and filling modification material, and matrix rubber is ethylene-octene copolymer; Its composition weight parts: (1) ethylene-octene copolymer: 100 parts; (2) filler reinforcing agent: 8.8-223 parts; (3) softening plasticizer: 1.7-100 parts; (4) anti-aging agent: 0.5-4 parts. The best range is: (1) ethylene-octene copolymer: 100 parts: (2) filling and reinforcing agent: 30-138 parts; (3) softening plasticizer: 30-60 parts; (4) anti-aging agent: 0.6 to 2 parts. It is also possible to add (5) activator: 5-7.5 parts; (6) cross-linking agent: 0.05-0.7 parts.

The ethylene-octene copolymer used in the present invention is a thermoplastic elastomer, which has thermoplastic processability and excellent anti-aging performance, but it must be added with filling reinforcing agent, softening Plasticizers and anti-aging agents are used to improve its processing shrinkage, poor heat resistance, and insufficient UV resistance, while effectively reducing costs. The ethylene-octene copolymer used in the present invention can be selected from the commercially available Engage product produced by DuPont-Dow Chemical Company, which is an ethylene-octene copolymer prepared by using a metallocene catalyst. This thermoplastic elastomer is a polymer with polyethylene crystalline phase (ie, plastic phase) and ethylene-octene amorphous region (ie, elastic phase) formed by arranging ethylene and octene from the point of view of molecular design. The number of carbon atoms is small, and its saturation is 100%, so it has good aging resistance. DuPont-Dow Chemical Company's Engage products are available in 8150, 8003, 8200, 8401 and other grades according to different hardness. The higher the hardness of Engage products, the higher the melting point, the higher the heat distortion temperature, and the lower the relative elasticity. As the hardness increases, the higher the crystallinity of Engage, the worse its ability to accommodate filler reinforcement and the less ability to absorb plasticizers. The consumption of ethylene-octene copolymer of the present invention is 100 parts (the following parts by weight are the same), when the consumption is too low, the filling reinforcing agent will form a continuous phase in the composition, thereby greatly increasing the elongation and elasticity of the sheet. Decline, cold resistance will not meet the requirements. If the amount of ethylene-octene copolymer is too high, its inherent defects in material properties will be exposed again, and the cost will also increase. The filling and reinforcing agent in the present invention solves the processing shrinkage problem of ethylene-octene polymer on the one hand, to improve processing performance, and improves the creep resistance, temperature resistance, UV resistance, Tear resistance. The filling reinforcing agent can be selected from well-known carbon black, white carbon black, calcium carbonate, clay or their mixtures. The amount of filling and reinforcing agent is mainly determined according to its type and the physical and mechanical properties of the waterproof membrane. It is generally controlled within the range of 8.8-223 parts, preferably within the range of 30-138 parts. Increasing the amount of filling and reinforcing agent can reduce the cost of waterproofing membranes, but excessive usage will deteriorate the flow properties of the rubber compound, and reduce the elongation and cold resistance of the material, and the flexibility of the membrane will also decrease. The softening plasticizer in the present invention can improve the processability of the ethylene-octene copolymer on the one hand, improve the fluidity, reduce the shrinkage rate, and enhance the infiltration and coating of the ethylene-octene copolymer to the filling reinforcing agent. On the other hand, it can also increase the elongation of the rubber compound, reduce the hardness of the rubber compound, and improve the cold resistance of the rubber compound. Various softening plasticizers conventionally used in rubber processing can be selected. According to the principle of similar polarity, the present invention selects paraffin oil, naphthenic oil or their mixtures. The dosage of the softening plasticizer is controlled in the range of 1.7-100 parts, preferably in the range of 30-60 parts. Too much softening plasticizer will reduce the strength of the rubber compound, and the heat resistance and creep resistance of the rubber compound will also deteriorate. The anti-aging agent (containing ultraviolet light absorbing agent) adopted in the present invention can further improve the anti-aging performance of the sizing material. Phenols, amine antioxidants or ultraviolet light absorbers used in conventional rubber can be selected. For example, commercially available antioxidant 1010, antioxidant 264, antioxidant DOPC or antioxidant 1076 are all available. The dosage is controlled within the range of 0.5-4 parts, preferably within the range of 0.6-2 parts.

An activator and a cross-linking agent can also be added to the composition of the above-mentioned waterproof membrane proposed by the present invention. The role of the activator is to increase the crosslinking speed and increase the crosslinking density. The activator can be a mixture of zinc oxide and stearic acid, the weight ratio of which is 1:1 to 5:1, 5 to 7.5 parts in total. The cross-linking agent can be selected from dicumyl peroxide, 2,5-dimethyl-2,5 bis(tert-butyl peroxy)hexane or di-tert-butyl peroxide. Since the crystalline phase of thermoplastic elastomer such as ethylene-octene copolymer is polyethylene phase, under the influence of thermal movement of polymer in the amorphous region, the melting point of this crystalline phase is low. Although filling reinforcing agents can effectively improve its thermal deformation resistance and increase its service temperature, it is still difficult to use it for a long time in an environment of 80°C to 100°C. A small amount of peroxide cross-linking agent is added to generate micro-crosslinking in the polymer phase during the mixing process. At this time, the thermoplasticity of the composition is not significantly affected, and at the same time, the thermal deformation resistance of the composition can be effectively improved. When too much peroxide crosslinking is added, the thermoplasticity of the polymer is significantly lost. The added amount of the peroxide crosslinking agent is controlled within the range of 0.05-0.7 parts.

Example 1

Composition parts by weight are:

base rubber

Engage 8150 100 copies

filler reinforcing agent

Carbon black (N330) 40 parts

Calcium carbonate 40 parts

softening plasticizer

naphthenic oil 25 parts

paraffin oil 15 parts

Antiaging agent

Antiaging agent

Antioxidant 1010 1 part of the above compounding system is mixed in an internal mixer, the mixing time is 3 to 15 minutes, the material temperature is 100°C to 120°C, and then rolled into sheets by a four-roll calender at 100°C to 120°C. Cool, roll and pack.

Example 2

base rubber

Engage 8150 100 copies

filler reinforcing agent

Carbon black (N330) 40 parts

Calcium carbonate 80 parts

softening plasticizer

Naphthenic oil 26 parts

paraffin oil 16 parts

Antiaging agent

The processing conditions of 2 parts of antioxidant 1010 are the same as in Example 1.

Example 3

base rubber

Engage 8150 100 copies

filler reinforcing agent

Carbon black (N330) 90 parts

Calcium carbonate 33 parts

softening plasticizer

Naphthenic oil 100 parts

Antiaging agent

0.5 parts of tert-butylphenyl salicylate processing conditions are the same as in Example 1.

Example 4

base rubber

Engage 8200 100 copies

filler reinforcing agent

Carbon black (N330) 40 parts

Clay 30 parts

softening plasticizer

Naphthenic oil 35 parts

paraffin oil 25 parts

Antiaging agent

0.6 parts of tert-butylphenyl salicylate The processing conditions are the same as in Example 1.

Example 5

base rubber

Engage 8003 100 copies

filler reinforcing agent

Carbon black (N330) 40 parts

Calcium carbonate 98 parts

softening plasticizer

naphthenic oil 30 parts

Antiaging agent

2 parts of processing conditions of tert-butylphenyl salicylate are the same as in Example 1.

Example 6

base rubber

Engage 8180 100 copies

filler reinforcing agent

Carbon black (N330) 43 parts

Calcium carbonate 52 parts

softening plasticizer

naphthenic oil 30 parts

Antiaging agent

Anti-aging agent 264 4 parts

active agent

Zinc oxide 5 parts

Stearic acid 2.5 parts

crosslinking agent

Dicumyl peroxide 0.7 part of the above compounding system is mixed in an internal mixer, and mixed at 150 ° C for 3 to 15 minutes to complete the required dynamic micro-crosslinking and mixing, at 100 ° C to 120 ° C with four The roll calender is rolled into sheet, cooled, rolled and packaged.

Example 7

base rubber

Engage 8003 100 copies

filler reinforcing agent

Calcium carbonate 8.8 parts

softening plasticizer

naphthenic oil 15 parts

Antiaging agent

Antioxidant 1010 0.6 parts The processing conditions are the same as in Example 1.

Example 8

base rubber

Engage 8200 100 copies

filler reinforcing agent

Carbon black (N330) 16 parts

Calcium carbonate 14 parts

softening plasticizer

Naphthenic oil 1.7 parts

Antiaging agent

Antiaging agent 264 1.9 parts

active agent

Zinc oxide 4 parts

Stearic acid 1 part

crosslinking agent

0.05 parts of dicumyl peroxide processing conditions are the same as embodiment 6

Example 9

base rubber

Engage 8003 100 copies

filler reinforcing agent

Carbon black (N330) 66 parts

Calcium carbonate 157 parts

softening plasticizer

paraffin oil 5 parts

Antiaging agent

Anti-aging agent 264 3 parts processing conditions are the same as embodiment 1. comparative example

base rubber

EPDM 100 parts

filler reinforcing agent

Quickly press out carbon black 20 parts

Hard clay 100 parts

softening plasticizer

Naphthenic oil 12.5 parts

Antiaging agent

Anti-aging agent C 1.5 parts

active agent

Zinc oxide 5 parts

Stearic acid 1.0 parts

Accelerator

Accelerator M 0.5 parts

Accelerator TMTD 1.5 parts

Cross-linking agent (sulfur) 2 parts of the above compounding system are mixed in an internal mixer for 15 to 25 minutes, then extruded with an extruder, and vulcanized with a drum vulcanizer at 160°C for 25 minutes. Cool, roll and pack.

The performance comparison of the waterproof membranes of the examples and comparative examples and the Ministry of Chemical Industry standard (HG2402-92) is listed in the table. It can be seen from the table that the performance index of the waterproof coiled material proposed by the present invention meets and exceeds the requirements of the HG2402-92 standard. Compared with the usual rubber-type waterproof membrane, it has the advantages of thermoplastic elastomer, does not need vulcanization process, the leftovers, waste materials and used products in the production process can be recycled, and the construction joints do not need special Adhesives are used for bonding, and thermal bonding can be used, so the cost is low. And in terms of performance, it is also better than EPDM thermosetting rubber waterproof membrane. It is a new type of waterproof membrane with excellent aging resistance and processing performance.

The performance comparison of embodiment and comparative example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 comparative example HG2402-92 First grade Qualified product Tensile strength (MPa) 11 9.5 8.0 8.4 11.2 10.8 twenty two 13.4 ≥8 ≥7 Elongation at break(%) 500 480 512 580 523 506 700 500 ≥450 Right Angle Tear Strength (KN/m) 37.4 33.8 37.2 35 47.5 39.6 50 30 ≥28 ≥24.5 Hot air aging condition: 80℃×168h Change rate of tensile strength, % change rate of elongation at break, % change rate of tear strength, % -7 -9 0 -4.7 -6.3 13 -18 -20 -20～40 -20～50 -6.4 -6.3 -7.8 -8.6 -5.2 -2 -8.6 -26.8 ≥-30 2.9 0.6 4.6 5.7 1.3 4.8 4 -3.3 -40～40 -50～50 Ozone aging (500pphm; 40℃×168h; elongation 40%, static) no crack no crack no crack no crack no crack no crack no crack no crack no crack no crack Brittle temperature (℃) -48 -50 -43 -48 -48 -48 -50 - -45 -40 Water impermeability (0.3MPa×30min) qualified qualified qualified qualified qualified qualified qualified qualified qualified qualified Processing methods thermoplastic, non-vulcanized thermoplastic, non-vulcanized thermoplastic, non-vulcanized thermoplastic, non-vulcanized thermoplastic, non-vulcanized thermoplastic, dynamically crosslinked thermoplastic, non-vulcanized thermosetting, vulcanized thermosetting, vulcanized thermosetting, vulcanized seam hot glue hot glue hot glue hot glue hot glue hot glue hot glue Adhesive Adhesive Adhesive Note: The data with * means ozone aging conditions: ozone aging (100pphm; 40℃×168h; elongation 40%, static)

Claims (2)

1. a thermoplastic rubber-type water-proof coiled material is made up of base rubber and filling-modified material,

It is characterized in that: base rubber is an ethylene-octene copolymer; It forms parts by weight: (1) ethylene-octene copolymer: 100 parts; (2) packing strengthening agent: 8.8-223 part; (3) softening softening agent: 1.7-100 part; (4) anti-aging agent: 0.5-4 part; Packing strengthening agent is carbon black, white carbon black, lime carbonate, potter's clay or their mixture; Softening softening agent is paraffin oil, naphthenic oil or their mixture; Anti-aging agent is phenolic type antioxidant, amines antioxidants or ultraviolet absorbers.

2. a thermoplastic rubber-type water-proof coiled material is made up of base rubber and filling-modified material,

It is characterized in that: base rubber is an ethylene-octene copolymer; It forms parts by weight: (1) ethylene-octene copolymer: 100 parts; (2) packing strengthening agent: 8.8-223 part; (3) softening softening agent: 1.7-100 part; (4) anti-aging agent: 0.5-4 part; (5) activator 5-7.5 part; (6) linking agent: 0.05-0.7 part; Packing strengthening agent is carbon black, white carbon black, lime carbonate, potter's clay or their mixture; Softening softening agent is paraffin oil, naphthenic oil or their mixture; Anti-aging agent is phenolic type antioxidant, amines antioxidants or ultraviolet absorbers; Activator is zinc oxide and stearic mixture; Linking agent is a dicumyl peroxide, 2,5-dimethyl-2,5 bis(t-butylperoxy) hexane or di-t-butyl peroxide.