CN106117721A - A kind of hard GSZ and preparation method thereof - Google Patents
A kind of hard GSZ and preparation method thereof Download PDFInfo
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- CN106117721A CN106117721A CN201610499877.9A CN201610499877A CN106117721A CN 106117721 A CN106117721 A CN 106117721A CN 201610499877 A CN201610499877 A CN 201610499877A CN 106117721 A CN106117721 A CN 106117721A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- Polyesters Or Polycarbonates (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention discloses a kind of hard GSZ, it is made up of the raw material of following weight parts: benzyl triphenyl phosphonium chloride phosphine 12, epoxy cotton seed oil acid butyl ester 46, graphene oxide 57, 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, manganese iso-octoate 0.1 0.3, polyoxyethylene oleic acid ester 0.8 1, aluminium-magnesium silicate 1.6 2, Methanamide 12, hydroxy stearic acid 0.7 1,8 copper quinolinate 0.4 1.The GSZ case hardness of the present invention is high, and crushing resistance is good.
Description
Technical field
The present invention relates to GSZ technical field, particularly relate to a kind of hard GSZ 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 hard GSZ and preparation side thereof
Method.
The present invention is achieved by the following technical solutions:
A kind of hard GSZ, it is made up of the raw material of following weight parts:
Benzyl triphenyl phosphonium chloride phosphine 1-2, epoxy cotton seed oil acid butyl ester 4-6, graphene oxide 5-7, 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, manganese iso-octoate
0.1-0.3, polyoxyethylene oleic acid ester 0.8-1, aluminium-magnesium silicate 1.6-2, Methanamide 1-2, hydroxy stearic acid 0.7-1,8-hydroxyl quinoline
Quinoline copper 0.4-1.
The preparation method of a kind of described hard GSZ, comprises the following steps:
(1) take the 60-70% of above-mentioned acetic anhydride weight, mix with P-hydroxybenzoic acid, hydroxy stearic acid, join 138-140 DEG C
Oil bath in, insulated and stirred 10-15 minute, drip compound weight 0.01-0.02%, the sulphuric acid of 96-98%, insulation reaction 3-
5 hours, 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 50-60 DEG C
In vacuum drying oven, 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, add above-mentioned 8-hydroxyquinoline
Copper, stirs, forced air drying, sends in the vacuum drying oven of 50-60 DEG C, is dried 20-24 hour, obtains acetylation monomer b；
(3) above-mentioned benzyl triphenyl phosphonium chloride phosphine is joined in the dehydrated alcohol of its weight 27-30 times, stir, add first
Amide, rises high-temperature 57-60 DEG C, insulated and stirred 4-10 minute, adds above-mentioned aluminium-magnesium silicate, manganese iso-octoate, 100-200 rev/min
Stir 18-20 minute, obtain amide alcohol 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 amide alcohol liquid, stir, add above-mentioned acetylation monomer a, acetylation monomer b, ultrasonic 30-40 minute, reduce pressure
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 Graphene Copolyester composite material is mixed with remaining each raw material, stir, send into extruder, through melted
Extrusion, melt is made sheet material by three roll squeezer roll-ins, then through punching, stretching, is obtained 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；The GSZ case hardness of the present invention is high, and crushing resistance is good.
Detailed description of the invention
A kind of hard GSZ, it is made up of the raw material of following weight parts:
Benzyl triphenyl phosphonium chloride phosphine 1, epoxy cotton seed oil acid butyl ester 4, graphene oxide 5, P-hydroxybenzoic acid 40, acetic anhydride 10,
Zinc acetate 0.08,6 hydroxynaphthoic acid 20, high density polyethylene (HDPE) 180, manganese iso-octoate 0.1, polyoxyethylene oleic acid ester 0.8, magnesium silicate
Aluminum 1.6, Methanamide 1, hydroxy stearic acid 0.7,8 copper quinolinate 0.4.
The preparation method of a kind of described hard GSZ, comprises the following steps:
(1) take the 60% of above-mentioned acetic anhydride weight, mix with P-hydroxybenzoic acid, hydroxy stearic acid, join the oil bath of 138 DEG C
In, insulated and stirred 10 minutes, drip compound weight 0.01%, the sulphuric acid of 96%, insulation reaction 3 hours, discharging, pour into while hot
In the frozen water of its weight 1.6 times, stand 3 minutes, forced air drying, send in the vacuum drying oven of 50 DEG C, be dried 20 hours,
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, adds above-mentioned 8 copper quinolinates, stir, drum
Air-dry dry, send in the vacuum drying oven of 50 DEG C, be dried 20 hours, obtain acetylation monomer b；
(3) above-mentioned benzyl triphenyl phosphonium chloride phosphine is joined in the dehydrated alcohol of its weight 27 times, stir, add formyl
Amine, rises high-temperature 57 DEG C, insulated and stirred 4 minutes, adds above-mentioned aluminium-magnesium silicate, manganese iso-octoate, and 100 revs/min are stirred 18 minutes,
Amide alcohol liquid；
(4) take above-mentioned graphene oxide, join in the dehydrated alcohol of its weight 100 times, ultrasonic disperse 50 minutes, add above-mentioned
Amide alcohol liquid, stirs, and adds above-mentioned acetylation monomer a, acetylation monomer b, and ultrasonic 30 minutes, decompression distillation, by product
It 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 Graphene Copolyester composite material is mixed with remaining each raw material, stir, send into extruder, through melted
Extrusion, melt is made sheet material by three roll squeezer roll-ins, then through punching, stretching, is obtained 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 hard GSZ, it is characterised in that it is made up of the raw material of following weight parts:
Benzyl triphenyl phosphonium chloride phosphine 1-2, epoxy cotton seed oil acid butyl ester 4-6, graphene oxide 5-7, 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, manganese iso-octoate
0.1-0.3, polyoxyethylene oleic acid ester 0.8-1, aluminium-magnesium silicate 1.6-2, Methanamide 1-2, hydroxy stearic acid 0.7-1,8-hydroxyl quinoline
Quinoline copper 0.4-1.
2. the preparation method of a hard GSZ as claimed in claim 1, it is characterised in that comprise the following steps:
(1) take the 60-70% of above-mentioned acetic anhydride weight, mix with P-hydroxybenzoic acid, hydroxy stearic acid, join 138-140 DEG C
Oil bath in, insulated and stirred 10-15 minute, drip compound weight 0.01-0.02%, the sulphuric acid of 96-98%, insulation reaction 3-
5 hours, 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 50-60 DEG C
In vacuum drying oven, 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, add above-mentioned 8-hydroxyquinoline
Copper, stirs, forced air drying, sends in the vacuum drying oven of 50-60 DEG C, is dried 20-24 hour, obtains acetylation monomer b；
(3) above-mentioned benzyl triphenyl phosphonium chloride phosphine is joined in the dehydrated alcohol of its weight 27-30 times, stir, add first
Amide, rises high-temperature 57-60 DEG C, insulated and stirred 4-10 minute, adds above-mentioned aluminium-magnesium silicate, manganese iso-octoate, 100-200 rev/min
Stir 18-20 minute, obtain amide alcohol 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 amide alcohol liquid, stir, add above-mentioned acetylation monomer a, acetylation monomer b, ultrasonic 30-40 minute, reduce pressure
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 Graphene Copolyester composite material is mixed with remaining each raw material, stir, send into extruder, through melted
Extrusion, melt is made sheet material by three roll squeezer roll-ins, then through punching, stretching, is obtained described GSZ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610499877.9A CN106117721A (en) | 2016-06-30 | 2016-06-30 | A kind of hard GSZ and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610499877.9A CN106117721A (en) | 2016-06-30 | 2016-06-30 | A kind of hard GSZ and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204738197U (en) * | 2015-07-01 | 2015-11-04 | 重庆大学 | Graphite alkene polymer combined material geogrid |
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- 2016-06-30 CN CN201610499877.9A patent/CN106117721A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204738197U (en) * | 2015-07-01 | 2015-11-04 | 重庆大学 | Graphite alkene polymer combined material geogrid |
Non-Patent Citations (2)
| 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 |
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