CN106117723A - A kind of Graphene strengthens GSZ and preparation method thereof - Google Patents
A kind of Graphene strengthens GSZ and preparation method thereof Download PDFInfo
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- CN106117723A CN106117723A CN201610499891.9A CN201610499891A CN106117723A CN 106117723 A CN106117723 A CN 106117723A CN 201610499891 A CN201610499891 A CN 201610499891A CN 106117723 A CN106117723 A CN 106117723A
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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
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
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- 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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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2207/06—Properties of polyethylene
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Abstract
The invention discloses a kind of Graphene and strengthen GSZ, it is made up of the raw material of following weight parts: barium metaborate 23, 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, isopropyl palmitate 12, ethoxylated alkylphenol ammonium sulfate 0.5 1, stannous chloride 1.6 2, polyglyceryl fatty acid ester 12, polyimides 0.4 1, polyadipate ethylene glycol 34, nickel sulfamic acid 0.1 0.2.The GSZ of the present invention has good surface strength and crushing resistance, and leakage resistance is good, the most perishable, and service life is long.
Description
Technical field
The present invention relates to GSZ technical field, particularly relate to a kind of Graphene and strengthen GSZ and preparation side thereof
Method.
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 Graphene strengthens GSZ and system thereof
Preparation Method.
The present invention is achieved by the following technical solutions:
A kind of Graphene strengthens GSZ, and it is made up of the raw material of following weight parts:
Barium metaborate 2-3, 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, isopropyl palmitate 1-2, ethoxylated alkylphenol ammonium sulfate
0.5-1, stannous chloride 1.6-2, polyglyceryl fatty acid ester 1-2, polyimides 0.4-1, polyadipate ethylene glycol 3-4, amino sulphur
Acid nickel 0.1-0.2.
A kind of described Graphene strengthens the preparation method of GSZ, comprises the following steps:
(1) above-mentioned nickel sulfamic acid is joined in P-hydroxybenzoic acid, rise high-temperature and be 50-60 DEG C, add above-mentioned ethyoxyl
Change alkyl phenol ammonium sulfate, insulated and stirred 3-4 minute, obtain pretreatment benzoic acid；
(2) take the 60-70% of above-mentioned acetic anhydride weight, mix with above-mentioned pretreatment benzoic acid, join the oil bath of 138-140 DEG C
In, insulated and stirred 10-15 minute, dropping compound weight 0.01-0.02%, the sulphuric acid of 96-98%, insulation reaction 3-5 hour,
Discharging, is poured in the frozen water of its weight 1.6-2 times while hot, stands 3-5 minute, forced air drying, and the vacuum sending into 50-60 DEG C is done
In dry case, it is dried 20-24 hour, obtains acetylation monomer a；
(3) 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 stannous chloride,
Stir, forced air drying, send in the vacuum drying oven of 50-60 DEG C, be dried 20-24 hour, obtain acetylation monomer b；
(4) being joined by above-mentioned isopropyl palmitate in the dehydrated alcohol of its weight 7-10 times, stir, rising high-temperature is
60-70 DEG C, adding barium metaborate, insulated and stirred 4-8 minute, add above-mentioned polyglyceryl fatty acid ester, stirring, to room temperature, obtains alcohol breast
Liquid；
(5) 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 emulsion, stir, be sequentially added into above-mentioned acetylation monomer a, acetylation monomer b, ultrasonic 30-40 minute, subtract
Pressure distillation, is dried product 20-25 hour under the vacuum of 60-70 DEG C, obtains monomer pretreating graphite alkene；
(6) 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；
(7) by above-mentioned Graphene Copolyester composite material, polyadipate ethylene glycol, polyimides mixing, it is incubated at 70-80 DEG C
Preheating 6-10 minute, mix with remaining each raw material, stir, send into extruder, through melt extruding, melt is by three roll squeezer rollers
It is pressed into sheet material, 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；The GSZ of the present invention has good surface strength and crushing resistance, and leakage resistance is good, the most perishable
Erosion, service life is long.
Detailed description of the invention
A kind of Graphene strengthens GSZ, and it is made up of the raw material of following weight parts:
Barium metaborate 2, graphene oxide 5, P-hydroxybenzoic acid 40, acetic anhydride 10, zinc acetate 0.08,6 hydroxynaphthoic acid 20, height
Density polyethylene 180, isopropyl palmitate 1, ethoxylated alkylphenol ammonium sulfate 0.5, stannous chloride 1.6, polyglycerol fatty acid
Ester 1, polyimides 0.4, polyadipate ethylene glycol 3, nickel sulfamic acid 0.1.
A kind of described Graphene strengthens the preparation method of GSZ, comprises the following steps:
(1) joining in P-hydroxybenzoic acid by above-mentioned nickel sulfamic acid, rising high-temperature is 50 DEG C, adds above-mentioned ethoxylation alkane
Base phenol ammonium sulfate, insulated and stirred 3 minutes, obtain pretreatment benzoic acid；
(2) take the 60% of above-mentioned acetic anhydride weight, mix with above-mentioned pretreatment benzoic acid, join in the oil bath of 138 DEG C, insulation
Stir 10 minutes, drip compound weight 0.01%, the sulphuric acid of 96%, insulation reaction 3 hours, discharging, be poured into it while hot heavy
Measure in the frozen water of 1.6 times, stand 3 minutes, forced air drying, send in the vacuum drying oven of 50 DEG C, be dried 20 hours, obtain acetylation
Monomer a；
(3) 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 stannous chloride, stir, and air blast is done
Dry, send in the vacuum drying oven of 50 DEG C, be dried 20 hours, obtain acetylation monomer b；
(4) being joined by above-mentioned isopropyl palmitate in the dehydrated alcohol of its weight 7 times, stir, rising high-temperature is 60 DEG C,
Adding barium metaborate, insulated and stirred 4 minutes, add above-mentioned polyglyceryl fatty acid ester, stirring, to room temperature, obtains alcohol emulsion；
(5) take above-mentioned graphene oxide, join in the dehydrated alcohol of its weight 100 times, ultrasonic disperse 50 minutes, add above-mentioned
Alcohol emulsion, stirs, and is sequentially added into above-mentioned acetylation monomer a, acetylation monomer b, and ultrasonic 30 minutes, decompression distillation, by product
Thing is dried 20 hours under the vacuum of 60 DEG C, obtains monomer pretreating graphite alkene；
(6) 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；
(7) by above-mentioned Graphene Copolyester composite material, polyadipate ethylene glycol, polyimides mixing, at 70 DEG C, insulation is pre-
Heat 6 minutes, mixes with remaining each raw material, stirs, send into extruder, and through melt extruding, melt is by three roll squeezer roll-in systems
Become sheet material, then through punching, stretching, obtain described GSZ.
Outward appearance: smooth, bubble-free, without groove mark；
The tensile yield strength of grid sheet: 22MPa；
Weld tensile strength: >=200N/cm.
Claims (2)
1. a Graphene strengthens GSZ, it is characterised in that it is made up of the raw material of following weight parts:
Barium metaborate 2-3, 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, isopropyl palmitate 1-2, ethoxylated alkylphenol ammonium sulfate
0.5-1, stannous chloride 1.6-2, polyglyceryl fatty acid ester 1-2, polyimides 0.4-1, polyadipate ethylene glycol 3-4, amino sulphur
Acid nickel 0.1-0.2.
2. the preparation method of a Graphene as claimed in claim 1 enhancing GSZ, it is characterised in that include following step
Rapid:
(1) above-mentioned nickel sulfamic acid is joined in P-hydroxybenzoic acid, rise high-temperature and be 50-60 DEG C, add above-mentioned ethyoxyl
Change alkyl phenol ammonium sulfate, insulated and stirred 3-4 minute, obtain pretreatment benzoic acid；
(2) take the 60-70% of above-mentioned acetic anhydride weight, mix with above-mentioned pretreatment benzoic acid, join the oil bath of 138-140 DEG C
In, insulated and stirred 10-15 minute, dropping compound weight 0.01-0.02%, the sulphuric acid of 96-98%, insulation reaction 3-5 hour,
Discharging, is poured in the frozen water of its weight 1.6-2 times while hot, stands 3-5 minute, forced air drying, and the vacuum sending into 50-60 DEG C is done
In dry case, it is dried 20-24 hour, obtains acetylation monomer a；
(3) 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 stannous chloride,
Stir, forced air drying, send in the vacuum drying oven of 50-60 DEG C, be dried 20-24 hour, obtain acetylation monomer b；
(4) being joined by above-mentioned isopropyl palmitate in the dehydrated alcohol of its weight 7-10 times, stir, rising high-temperature is
60-70 DEG C, adding barium metaborate, insulated and stirred 4-8 minute, add above-mentioned polyglyceryl fatty acid ester, stirring, to room temperature, obtains alcohol breast
Liquid；
(5) 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 emulsion, stir, be sequentially added into above-mentioned acetylation monomer a, acetylation monomer b, ultrasonic 30-40 minute, subtract
Pressure distillation, is dried product 20-25 hour under the vacuum of 60-70 DEG C, obtains monomer pretreating graphite alkene；
(6) 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；
(7) by above-mentioned Graphene Copolyester composite material, polyadipate ethylene glycol, polyimides mixing, it is incubated at 70-80 DEG C
Preheating 6-10 minute, mix with remaining each raw material, stir, send into extruder, through melt extruding, melt is by three roll squeezer rollers
It is pressed into sheet material, then through punching, stretching, obtains described GSZ.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610499891.9A CN106117723A (en) | 2016-06-30 | 2016-06-30 | A kind of Graphene strengthens GSZ and preparation method thereof |
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| CN201610499891.9A CN106117723A (en) | 2016-06-30 | 2016-06-30 | A kind of Graphene strengthens 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 CN201610499891.9A patent/CN106117723A/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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