CN106117722A - A kind of rubber and plastic compound geogrid and preparation method thereof - Google Patents

A kind of rubber and plastic compound geogrid and preparation method thereof Download PDF

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Publication number
CN106117722A
CN106117722A CN201610499880.0A CN201610499880A CN106117722A CN 106117722 A CN106117722 A CN 106117722A CN 201610499880 A CN201610499880 A CN 201610499880A CN 106117722 A CN106117722 A CN 106117722A
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minute
rubber
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叶磊
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ANHUI JIEAO MAKE COMPOSITES TECHNOLOGY Co Ltd
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ANHUI JIEAO MAKE COMPOSITES TECHNOLOGY Co Ltd
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Priority to CN201610499880.0A priority Critical patent/CN106117722A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • C08G63/82Preparation processes characterised by the catalyst used
    • C08G63/83Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/062HDPE

Abstract

The invention discloses a kind of rubber and plastic compound geogrid, it is made up of the raw material of following weight parts: trimethylolpropane 0.6 1, ethylene propylene diene rubber 14 17, ammonium hydrogen carbonate 12, P-hydroxybenzoic acid 40 50, acetic anhydride 10 17, zinc acetate 0.08 0.1,6 hydroxyl 2 naphthoic acid 20 30, high density polyethylene (HDPE) 180 200, sym-closene 0.6 1, palm wax 35, oleic acid potash soap 12, di-2-ethylhexyl maleate 68, alkanolamide 0.7 1, benzotriazole 12, zinc ricinate 12, graphene oxide 57, sorbitan monooleate 0.6 1.Present invention adds ethylene propylene diene rubber, effectively raise surface resistive and the weatherability of finished-product material.

Description

A kind of rubber and plastic compound geogrid and preparation method thereof
Technical field
The present invention relates to GSZ technical field, particularly relate to a kind of rubber and plastic compound geogrid and preparation method thereof.
Background technology
Thermotropic Liquid has the combination property of excellence, such as high intensity, high-modulus, good heat stability and one-tenth Type processing characteristics etc. so that it is can be widely applied for the new and high technologies such as space flight and aviation, defence and military, fiber optic communication, electronic apparatus Field.Although Thermotropic Liquid has the combination property of excellence, but this material is proposed higher by the development of science and technology Requirement, especially needs it to have higher modulus, intensity and heat stability etc. at some special dimensions.It is thus desirable to thermic Liquid crystal copolyesters ester material is modified, and numerous studies show the nano materials such as CNT, nano carbon black and carbon nano-fiber all Can effectively improve the performance of Thermotropic Liquid, especially mechanical property and thermal stability.Graphene is as one Emerging two-dimensional nano material with carbon element, has more excellent compared with the nano materials such as CNT, nano carbon black and carbon nano-fiber Different performance, and it also embodies the biggest potentiality when other polymer modified.
A small amount of document is had to carry out report with regard to Graphene modification Thermotropic Liquid.Root according to the literature, prepares thermic The technique of liquid crystal copolyester/graphene composite material used in-situ solution polymerization, needs to consume greatly in preparation process Amount solvent, is unfavorable for environmental conservation, and the Thermotropic Liquid/Graphene prepared by the way of in-situ solution is polymerized is multiple The mechanical property of condensation material is bad, it is impossible to meet the requirement of reality application;.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of rubber and plastic compound geogrid and preparation thereof Method.
The present invention is achieved by the following technical solutions:
A kind of rubber and plastic compound geogrid, it is made up of the raw material of following weight parts:
Trimethylolpropane 0.6-1, ethylene propylene diene rubber 14-17, ammonium hydrogen carbonate 1-2, P-hydroxybenzoic acid 40-50, acetic anhydride 10-17, zinc acetate 0.08-0.1,6-Hydroxy-2-naphthoic acid 20-30, high density polyethylene (HDPE) 180-200, sym-closene 0.6-1, palm wax 3-5, oleic acid potash soap 1-2, di-2-ethylhexyl maleate 6-8, alkanolamide 0.7-1, benzotriazole 1-2, Semen Ricini Zinc oleate 1-2, graphene oxide 5-7, sorbitan monooleate 0.6-1.
The preparation method of a kind of described rubber and plastic compound geogrid, comprises the following steps:
(1) take the 60-70% of above-mentioned acetic anhydride weight, mix with P-hydroxybenzoic acid, join in the oil bath of 138-140 DEG C, protect Temperature stirring 10-15 minute, dropping compound weight 0.01-0.02%, the sulphuric acid of 96-98%, insulation reaction 3-5 hour, discharging, It is poured into while hot in the frozen water of its weight 1.6-2 times, stands 3-5 minute, forced air drying, send into the vacuum drying oven of 50-60 DEG C In, it is dried 20-24 hour, obtains acetylation monomer a;
(2) by above-mentioned 6-Hydroxy-2-naphthoic acid, the mixing of remaining acetic anhydride, joining in the oil bath of 120-130 DEG C, insulation is anti- Answer 3-4 hour, discharging, be poured into while hot in the frozen water of its weight 1.6-2 times, stand 3-5 minute, forced air drying, send into 50-60 DEG C vacuum drying oven in, be dried 20-24 hour, obtain acetylation monomer b;
(3) above-mentioned benzotriazole is joined in the dehydrated alcohol of its weight 20-34 times, stir, add above-mentioned Petiolus Trachycarpi Wax, rises high-temperature and is 70-80 DEG C, and insulated and stirred 3-5 minute adds ammonium hydrogen carbonate, stirs, obtain alcohol dispersion liquid;
(4) take above-mentioned graphene oxide, join in the dehydrated alcohol of its weight 100-120 times, ultrasonic disperse 50-60 minute, Add above-mentioned alcohol dispersion liquid, stir, be sequentially added into above-mentioned acetylation monomer a, acetylation monomer b, ultrasonic 30-40 minute, Decompression distillation, is dried product 20-25 hour under the vacuum of 60-70 DEG C, obtains monomer pretreating graphite alkene;
(5) by above-mentioned monomer pretreating graphite alkene, zinc acetate mixing, it is sent in reactor, is passed through nitrogen protection, rises high-temperature For 240-250 DEG C, insulation reaction 3-4 hour, continue to rise high-temperature and be 270-280 DEG C, insulation reaction 1-2 hour, continues to raise Temperature is 290-300 DEG C, insulation reaction 30-40 minute, and discharging cools down, and obtains Graphene Copolyester composite material;
(6) above-mentioned sorbitan monooleate is joined in the deionized water of its weight 30-40 times, stir, add alkanol Amide, stirs, and obtains amide dispersion liquid;
(7) above-mentioned zinc ricinate is joined in the dehydrated alcohol of its weight 27-30 times, stir, add EPDM Rubber, sends in the water-bath of 60-70 DEG C, adds above-mentioned amide dispersion liquid, insulated and stirred 10-20 minute, adds above-mentioned Graphene Copolyester composite material, stirs, discharging, filters, and is vacuum dried 1-2 hour, will obtain modified graphite at being deposited in 50-60 DEG C Alkene Copolyester composite material;
(8) above-mentioned modified graphene Copolyester composite material is mixed with remaining each raw material, stir, send into extruder, warp Melt extruding, melt is made sheet material by three roll squeezer roll-ins, then through punching, stretching, obtains described GSZ.
The invention have the advantage that the present invention uses P-hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid to be monomer, pass through sulphuric acid Carry out acetylation process with acetic anhydride under catalytic action, then acetylation monomer is carried out melt polymerization, lead in the course of the polymerization process Peracetic acid zinc is catalyzed, and obtains the polyester with strand cross-linked network structure, and the present invention adds oxidation the most in the course of the polymerization process Graphene, its surface contains the oxy radicals such as substantial amounts of hydroxyl, carboxyl, epoxy radicals, and the existence of oxy radical can make graphite flake layer Spacing expands so that it is can be good be dispersed in polymeric matrix, thus effectively improves finished product Thermotropic Liquid Mechanical property, and on the one hand the raising of mechanical property is come from polyester molecule chain and is connected on graphene oxide lamella by ester group, On the other hand the non-covalent bond effect of the aromatic rings in Thermotropic Liquid strand and graphene oxide sheet interlayer is come from, and The Graphene Copolyester composite material obtained is due to the physical barrier effect of graphene oxide, the expansion of the thermal degradation products that slowed down Dissipate, therefore there is good melt fluidity, and then can well be distributed in polypropylene, obtain polymolecularity, without particle The finished-product material reunited;Present invention adds ethylene propylene diene rubber, effectively raise the surface resistive of finished-product material and weather-proof Property.
Detailed description of the invention
A kind of rubber and plastic compound geogrid, it is made up of the raw material of following weight parts:
Trimethylolpropane 0.6, ethylene propylene diene rubber 14, ammonium hydrogen carbonate 1, P-hydroxybenzoic acid 40, acetic anhydride 10, zinc acetate 0.08,6 hydroxynaphthoic acids 20, high density polyethylene (HDPE) 180, sym-closene 0.6, palm wax 3, oleic acid potash soap 1, maleic acid two Monooctyl ester 6, alkanolamide 0.7, benzotriazole 1, zinc ricinate 1, graphene oxide 5, sorbitan monooleate 0.6.
The preparation method of a kind of described rubber and plastic compound geogrid, comprises the following steps:
(1) take the 60% of above-mentioned acetic anhydride weight, mix with P-hydroxybenzoic acid, join in the oil bath of 138 DEG C, insulated and stirred 10 minutes, drip compound weight 0.01%, the sulphuric acid of 96%, insulation reaction 3 hours, discharging, be poured into its weight 1.6 while hot In frozen water again, stand 3 minutes, forced air drying, send in the vacuum drying oven of 50 DEG C, be dried 20 hours, obtain acetylation monomer a;
(2) by above-mentioned 6 hydroxynaphthoic acids, the mixing of remaining acetic anhydride, join in the oil bath of 120 DEG C, insulation reaction 3 hours, Discharging, is poured in the frozen water of its weight 1.6 times while hot, stands 3 minutes, forced air drying, sends in the vacuum drying oven of 50 DEG C, It is dried 20 hours, obtains acetylation monomer b;
(3) above-mentioned benzotriazole is joined in the dehydrated alcohol of its weight 20 times, stirs, add above-mentioned palm wax, Rising high-temperature is 70 DEG C, and insulated and stirred 3 minutes adds ammonium hydrogen carbonate, stirs, obtain alcohol dispersion liquid;
(4) take above-mentioned graphene oxide, join in the dehydrated alcohol of its weight 100 times, ultrasonic disperse 50 minutes, add above-mentioned Alcohol dispersion liquid, stirs, and is sequentially added into above-mentioned acetylation monomer a, acetylation monomer b, and ultrasonic 30 minutes, decompression was distilled, will Product is dried 20 hours under the vacuum of 60 DEG C, obtains monomer pretreating graphite alkene;
(5) by above-mentioned monomer pretreating graphite alkene, zinc acetate mixing, it is sent in reactor, is passed through nitrogen protection, rises high-temperature It is 240 DEG C, insulation reaction 3 hours, continuing to rise high-temperature is 270 DEG C, insulation reaction 1 hour, and continuing to rise high-temperature is 290 DEG C, Insulation reaction 30 minutes, discharging cools down, obtains Graphene Copolyester composite material;
(6) above-mentioned sorbitan monooleate is joined in the deionized water of its weight 30 times, stir, add alkanol acyl Amine, stirs, and obtains amide dispersion liquid;
(7) above-mentioned zinc ricinate is joined in the dehydrated alcohol of its weight 27 times, stir, add ethylene-propylene-diene monomer Glue, sends in the water-bath of 60 DEG C, adds above-mentioned amide dispersion liquid, insulated and stirred 10 minutes, adds above-mentioned Graphene copolyesters multiple Condensation material, stirs, discharging, filters, and will be deposited at 50 DEG C vacuum drying 1 hour, obtains modified graphene copolyesters and is combined Material;
(8) above-mentioned modified graphene Copolyester composite material is mixed with remaining each raw material, stir, send into extruder, warp Melt extruding, melt is made sheet material by three roll squeezer roll-ins, then through punching, stretching, obtains described GSZ.
Outward appearance: smooth, bubble-free, without groove mark;
The tensile yield strength of grid sheet: 25MPa;
Weld tensile strength: >=200N/cm.

Claims (2)

1. a rubber and plastic compound geogrid, it is characterised in that it is made up of the raw material of following weight parts:
Trimethylolpropane 0.6-1, ethylene propylene diene rubber 14-17, ammonium hydrogen carbonate 1-2, P-hydroxybenzoic acid 40-50, acetic anhydride 10-17, zinc acetate 0.08-0.1,6-Hydroxy-2-naphthoic acid 20-30, high density polyethylene (HDPE) 180-200, sym-closene 0.6-1, palm wax 3-5, oleic acid potash soap 1-2, di-2-ethylhexyl maleate 6-8, alkanolamide 0.7-1, benzotriazole 1-2, Semen Ricini Zinc oleate 1-2, graphene oxide 5-7, sorbitan monooleate 0.6-1.
2. the preparation method of a rubber and plastic compound geogrid as claimed in claim 1, it is characterised in that include following step Rapid:
(1) take the 60-70% of above-mentioned acetic anhydride weight, mix with P-hydroxybenzoic acid, join in the oil bath of 138-140 DEG C, protect Temperature stirring 10-15 minute, dropping compound weight 0.01-0.02%, the sulphuric acid of 96-98%, insulation reaction 3-5 hour, discharging, It is poured into while hot in the frozen water of its weight 1.6-2 times, stands 3-5 minute, forced air drying, send into the vacuum drying oven of 50-60 DEG C In, it is dried 20-24 hour, obtains acetylation monomer a;
(2) by above-mentioned 6-Hydroxy-2-naphthoic acid, the mixing of remaining acetic anhydride, joining in the oil bath of 120-130 DEG C, insulation is anti- Answer 3-4 hour, discharging, be poured into while hot in the frozen water of its weight 1.6-2 times, stand 3-5 minute, forced air drying, send into 50-60 DEG C vacuum drying oven in, be dried 20-24 hour, obtain acetylation monomer b;
(3) above-mentioned benzotriazole is joined in the dehydrated alcohol of its weight 20-34 times, stir, add above-mentioned Petiolus Trachycarpi Wax, rises high-temperature and is 70-80 DEG C, and insulated and stirred 3-5 minute adds ammonium hydrogen carbonate, stirs, obtain alcohol dispersion liquid;
(4) take above-mentioned graphene oxide, join in the dehydrated alcohol of its weight 100-120 times, ultrasonic disperse 50-60 minute, Add above-mentioned alcohol dispersion liquid, stir, be sequentially added into above-mentioned acetylation monomer a, acetylation monomer b, ultrasonic 30-40 minute, Decompression distillation, is dried product 20-25 hour under the vacuum of 60-70 DEG C, obtains monomer pretreating graphite alkene;
(5) by above-mentioned monomer pretreating graphite alkene, zinc acetate mixing, it is sent in reactor, is passed through nitrogen protection, rises high-temperature For 240-250 DEG C, insulation reaction 3-4 hour, continue to rise high-temperature and be 270-280 DEG C, insulation reaction 1-2 hour, continues to raise Temperature is 290-300 DEG C, insulation reaction 30-40 minute, and discharging cools down, and obtains Graphene Copolyester composite material;
(6) above-mentioned sorbitan monooleate is joined in the deionized water of its weight 30-40 times, stir, add alkanol Amide, stirs, and obtains amide dispersion liquid;
(7) above-mentioned zinc ricinate is joined in the dehydrated alcohol of its weight 27-30 times, stir, add EPDM Rubber, sends in the water-bath of 60-70 DEG C, adds above-mentioned amide dispersion liquid, insulated and stirred 10-20 minute, adds above-mentioned Graphene Copolyester composite material, stirs, discharging, filters, and is vacuum dried 1-2 hour, will obtain modified graphite at being deposited in 50-60 DEG C Alkene Copolyester composite material;
(8) above-mentioned modified graphene Copolyester composite material is mixed with remaining each raw material, stir, send into extruder, warp Melt extruding, melt is made sheet material by three roll squeezer roll-ins, then through punching, stretching, obtains described GSZ.
CN201610499880.0A 2016-06-30 2016-06-30 A kind of rubber and plastic compound geogrid and preparation method thereof Pending CN106117722A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104292642A (en) * 2014-10-25 2015-01-21 安徽杰奥玛克合成材料科技有限公司 Ethylene propylene diene monomer modified geogrid and preparation method thereof
CN204738197U (en) * 2015-07-01 2015-11-04 重庆大学 Graphite alkene polymer combined material geogrid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104292642A (en) * 2014-10-25 2015-01-21 安徽杰奥玛克合成材料科技有限公司 Ethylene propylene diene monomer modified geogrid and preparation method thereof
CN204738197U (en) * 2015-07-01 2015-11-04 重庆大学 Graphite alkene polymer combined material geogrid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李宗昊: "热致液晶共聚酯/氧化石墨烯复合材料的制备及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *
薛敏: "塑料土工格栅的生产开发", 《现代塑料加工应用》 *

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Application publication date: 20161116