CN109280348A - A kind of wear-resisting, high-strength PC TG composite material and preparation method - Google Patents
A kind of wear-resisting, high-strength PC TG composite material and preparation method Download PDFInfo
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- CN109280348A CN109280348A CN201811113419.2A CN201811113419A CN109280348A CN 109280348 A CN109280348 A CN 109280348A CN 201811113419 A CN201811113419 A CN 201811113419A CN 109280348 A CN109280348 A CN 109280348A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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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
- 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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- 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
- C08L2207/068—Ultra high molecular weight polyethylene
Abstract
The invention discloses a kind of wear-resisting, high-strength PC TG composite materials, including following parts by weight of component: 30~75 parts of PCTG resin, 15~50 parts of glass fibre, 5~15 parts of carbon fiber, 0~15 part of polytetrafluoroethylene powder, 0~10 part of ultra-high molecular weight polyethylene, 2~10 parts of molybdenum disulfide；And suitable processing aid；It is described it is carbon fiber loaded have silicon dioxide microsphere, the glass fibre is by silane-modified.Invention also improves the preparation methods of above-mentioned PCTG composite material.PCTG composite material of the invention has the advantages that wear-resistant strength is high.
Description
Technical field
The present invention relates to polymeric material field, especially a kind of wear-resisting, high-strength PC TG composite material and its preparation side
Method.
Background technique
With the development of science and technology, general-purpose plastics can not meet the demand of social development in certain fields.In recent years
Come, engineering plastics are widely used, and PCTG has also obtained the concern of height, and PCTG has excellent thermal stability, height
Toughness, corrosion resistance and electrical property, while also there is good mechanical property and dimensional stability, it is widely used in electronics electricity
The fields such as gas, machine-building, automobile manufacture, chemical industry instrument and meter and aerospace industry.
But there are also disadvantages by PCTG, and such as: the PCTG intensity of copolymerization is low, and wear-resisting property is poor；The Tg of pars amorpha
It is lower, using temperature for a long time more than 90 DEG C when be also easy to produce creep, higher cost etc..These determinations limit the application model of PCTG
It encloses.
Summary of the invention
The first purpose of this invention is to provide with excellent low temperature impact properties, high intensity, high-modulus, thermostabilization
Property, the molding PCTG composite material of easy processing.
Second object of the present invention is to provide the preparation method of above-mentioned PCTG composite material.
In order to realize that first purpose, previous technical solution provided by the invention are such that a kind of wear-resisting, high-intensitive
PCTG composite material, including following parts by weight of component: 30~75 parts of PCTG resin, 15~50 parts of glass fibre, carbon fiber 5~15
Part, 0~15 part of polytetrafluoroethylene powder, 0~10 part of ultra-high molecular weight polyethylene, 2~10 parts of molybdenum disulfide；And suitable processing
Auxiliary agent；
It is described it is carbon fiber loaded have silicon dioxide microsphere, the glass fibre is by silane-modified.
The carbon fiber loaded preparation method for having silicon dioxide microsphere has been technological means commonly used in the art, such as
A kind of method of surface modification of silica carbon fiber disclosed in CN201410809082.4；Silane-modified glass fibre
Preparation method can refer to CN201510872072.X glass fibre method of modifying and its application.
It further include 0~15 part of polytetrafluoroethylene powder, molybdenum disulfide 2 in above-mentioned wear-resisting, high-strength PC TG composite material
~10 parts, 0.2~1.5 part of coupling agent, 0.2~1 part of antioxidant, 0.1~0.5 part of the steady agent of light；5-10 parts of hydroxy silicon oil；Toughener
3-20 parts；0.2~2 part of processing aid；
Wherein, the polytetrafluoroethylene powder molecular weight is less than 10,000, and partial size is at 0.5~15 μm；Ultra-high molecular weight polyethylene point
Son amount is greater than 1,500,000；Molybdenum disulfide is 1250 mesh.
In above-mentioned wear-resisting, high-strength PC TG composite material, the hydroxy silicon oil viscosity is 30~50mpa/s, hydroxyl
Base molar content is 5~10%.
In above-mentioned wear-resisting, high-strength PC TG composite material, the toughener is ethylene-methyl acrylate-methyl
Glycidyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-octene copolymer grafted maleic anhydride, ternary
Isopropyl grafting rubbers maleic anhydride, ethylene-vinyl acetate copolymer, styrene-hydrogenated butadiene polymer-styrene block copolymer
One or more of mixture.
In above-mentioned wear-resisting, high-strength PC TG composite material, the coupling agent is that silane coupling agent, Aluminate are coupled
Agent, titanate coupling agent or zirconium ester coupling agent；The silane coupling agent is 3- aminopropyl triethoxysilane, γ-(2,3-
The third oxygen of epoxy) propyl trimethoxy silicane, the mixing of one or more of γ-(methacryloxypropyl) propyl trimethoxy silicane
Object；Titanate coupling agent is isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl dioleate oxygroup (dioctyl
Phosphoric acid acyloxy titanate esters), one or more of isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters mixture；Zirconate
Coupling agent is zirconium-n-propylate；Aluminate coupling agent is three isopropyl ester of aluminic acid.
In above-mentioned wear-resisting, high-strength PC TG composite material, the antioxidant is phenols, amine, phosphorous acid esters, sulphur
For one or more of esters, matal deactivator mixture；
The phenolic antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and four [β-
One or both of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester；Amine antioxidants are octylatcd hexichol
Amine and N, one or both of N '-diisooctyl p-phenylenediamine；Phosphite ester antioxidant is three [2,4- di-tert-butyls
Base] phosphite ester；Thioester antioxidant is one in thio-2 acid double octadecyls and thiodipropionic acid bis-dodecanol ester
Kind or two kinds；Matal deactivator is N, bis- salicylidene propane diamine of N'-.
It is the processing aid silicone powder, calcium stearate, hard in above-mentioned wear-resisting, high-strength PC TG composite material
Resin acid zinc, dimethicone, N, one or more of N '-ethylene bis stearamide mixture；The steady agent of light is Ketene dimethyl
One or both of class and hindered amines mixture；The steady agent of diformazan ketone light is 2- [4- [2- hydroxyl -3- tridecane oxygen
Base propyl] oxygroup] -2- hydroxy phenyl] bis- (2,4- the 3,5-dimethylphenyl) -1,3,5- triazines of -4,6- and 2- [4- [2- hydroxyl -3- ten
Dialkyloxypropyl] oxygroup] -2- hydroxy phenyl] bis- (2,4- the 3,5-dimethylphenyl) -1,3,5- triazine mixtures of -4,6-；Hindered amine
The steady agent of class light is poly-succinic (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine ethanol) ester.
In addition, the invention also discloses a kind of wear-resisting, high-strength PC TG composite material preparation method as described above, packet
Include following steps:
Step 1: proportionally weighing each raw material component；
Step 2: PCTG resin is 5 hours dry at 105 DEG C；
Step 3: other components will be uniformly mixed, and be placed in double screw extruder in addition to glass fibre and carbon fiber, and squeeze
Glass fibre and carbon fiber is added in machine downstream out, obtains product by melting, mixing, extrusion, cooling, drying, pelletizing；The step
The temperature melted in rapid 3 is 223~237 DEG C.
Compared with prior art, PCTG composite material of the invention is by using above-mentioned raw materials, phase interworking between each raw material
Cooperation is used, concerted reaction, and low temperature impact properties, high intensity, high-modulus, thermal stability, easy processing molding have obtained effectively
Promotion.
Wherein, by carbon fiber loaded silicon dioxide microsphere and glass fibre by silane-modified and PCTG resin phase interworking
It closes, to enhance the wearability of composite material.
The present invention uses matrix resin of non-crystalline copolyester PCTG as composite material, reduces polyester composite wood
Difference in shrinkage when material molding in flowing and perpendicular flow direction, can effectively reduce 90% or more of product warpage degree, and
The excellent mechanical property of fibre-glass reinforced polyester composite material is maintained, while raw material types are less, is convenient for selection and reality
Border production operation, the present invention have broad application prospects in molding complexity, thin wall product field.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, but described embodiment
It is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel all other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
In the case where not doing specified otherwise, following components are parts by weight.
Embodiment 1
A kind of wear-resisting, high-strength PC TG composite material, material composition are as follows:
50 parts of PCTG resin, 30 parts of glass fibre, 10 parts of carbon fiber, 8 parts of molybdenum disulfide；10 parts of polytetrafluoroethylene powder, two
7 parts of molybdenum sulfide, 1 part of 3- aminopropyl triethoxysilane, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester
0.5 part, 2- [4- [2- hydroxyl -3- tridecane epoxide propyl] oxygroup] -2- hydroxy phenyl] -4,6- bis- (2,4- 3,5-dimethylphenyls) -
0.2 part of 1,3,5- triazine；5 parts of maleic anhydride of ternary isopropyl grafting rubbers；0.5 part of silicone powder；0.5 part of zinc stearate.
Wherein, molybdenum disulfide is 1250 mesh；Polytetrafluoroethylene powder molecular weight is less than 10,000, and partial size is at 0.5~15 μm；
PCTG composite material the preparation method comprises the following steps:
Step 1: proportionally weighing each raw material component；
Step 2: PCTG resin is 5 hours dry at 105 DEG C；
Step 3: other components will be uniformly mixed, and be placed in double screw extruder in addition to glass fibre and carbon fiber, and squeeze
Glass fibre and carbon fiber is added in machine downstream out, obtains product by melting, mixing, extrusion, cooling, drying, pelletizing；The step
The temperature melted in rapid 3 is 223~237 DEG C.
Embodiment 2
A kind of wear-resisting, high-strength PC TG composite material, material composition are as follows:
30 parts of PCTG resin, 50 parts of glass fibre, 15 parts of carbon fiber, 10 parts of polytetrafluoroethylene powder；8 parts of molybdenum disulfide；It is super
8 parts of High molecular weight polyethylene；1.2 parts of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, three [2,4- di-tert-butyls
Base] 0.8 part of phosphite ester, 15 parts of maleic anhydride of ternary isopropyl grafting rubbers；Succinic acid (4- hydroxyl -2,2,6,6- tetramethyl -1-
Piperidine ethanol) 0.2 part of ester；0.5 part of silicone powder；0.5 part of zinc stearate.
Wherein, molybdenum disulfide is 1250 mesh；Polytetrafluoroethylene powder molecular weight is less than 10,000, and partial size is at 0.5~15 μm；Superelevation
Molecular weight polyethylene molecular weight is greater than 1,500,000；
The preparation method is the same as that of Example 1 for PCTG composite material.
Embodiment 3
A kind of wear-resisting, high-strength PC TG composite material, material composition are as follows:
70 parts of PCTG resin, 20 parts of glass fibre, 10 parts of carbon fiber, 5 parts of polytetrafluoroethylene powder；10 parts of molybdenum disulfide；It is super
10 parts of High molecular weight polyethylene；1.2 parts of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, three [2,4- di-tert-butyls
Base] 0.8 part of phosphite ester, 0 part of ethylene-methyl acrylate-glyceryl methacrylate copolymer 1, poly-succinic (4- hydroxyl
Base -2,2,6,6- tetramethyl -1- piperidine ethanol) 0.2 part of ester；0.5 part of silicone powder；0.5 part of zinc stearate.
Wherein, molybdenum disulfide is 1250 mesh；Polytetrafluoroethylene powder molecular weight is less than 10,000, and partial size is at 0.5~15 μm；Superelevation
Molecular weight polyethylene molecular weight is greater than 1,500,000；
The preparation method is the same as that of Example 1 for PCTG composite material.
Embodiment 4
A kind of wear-resisting, high-strength PC TG composite material, material composition are as follows:
45 parts of PCTG resin, 15 parts of glass fibre, 13 parts of carbon fiber, 8 parts of polytetrafluoroethylene powder；3 parts of molybdenum disulfide；Superelevation
8 parts of molecular weight polyethylene；0.4 part of three isopropyl ester of aluminic acid, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
0.8 part of ester, 20 parts of ethylene-butyl acrylate copolymer, 2- [4- [2- hydroxyl -3- tridecane epoxide propyl] oxygroup] -2- hydroxyl
Phenyl] 0.3 part of -1,3,5- triazine of -4,6- bis- (2,4- 3,5-dimethylphenyls)；0.5 part of N, N '-ethylene bis stearamide.
Wherein, molybdenum disulfide is 1250 mesh；Polytetrafluoroethylene powder molecular weight is less than 10,000, and partial size is at 0.5~15 μm；Superelevation
Molecular weight polyethylene molecular weight is greater than 1,500,000；
The preparation method is the same as that of Example 1 for PCTG composite material.
Embodiment 5
A kind of wear-resisting, high-strength PC TG composite material, material composition are as follows:
45 parts of PCTG resin, 15 parts of glass fibre, 13 parts of carbon fiber, 3 parts of molybdenum disulfide；8 parts of ultra-high molecular weight polyethylene；
0.4 part of three isopropyl ester of aluminic acid, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] 0.8 part of pentaerythritol esters, ethylene-the third
20 parts of olefin(e) acid acrylate copolymer, 2- [4- [2- hydroxyl -3- tridecane epoxide propyl] oxygroup] -2- hydroxy phenyl] -4,6- it is bis- (2,
4- 3,5-dimethylphenyl) 0.3 part of -1,3,5- triazine；0.5 part of N, N '-ethylene bis stearamide.
Wherein, molybdenum disulfide is 1250 mesh；Partial size is at 0.5~15 μm；Ultra-high molecular weight polyethylene molecular weight is greater than 150
Ten thousand；
The preparation method is the same as that of Example 1 for PCTG composite material.
Comparative example 1
It is substantially the same with embodiment 4, different places is, carbon fiber does not have nonloaded silica, and glass fibre does not have
By silane-modified.
Comparative example 2
It is substantially the same with embodiment 4, different places is, not carbon fiber-containing, is by silane-modified glass fibre
28 parts.
Comparative example 3
It is substantially the same with embodiment 4, different places is, is free of glass fibre, and the carbon fiber of nonloaded silica is
28 parts.
PCTG composite material made from embodiment 1-5 and comparative example 1-3 is subjected to following performance test:
The test of low temperature falling sphere: after test piece is adjusted 4h under the conditions of -30 DEG C, the test of low temperature falling sphere is carried out, size of sample is
Thick 2.5mm, width 100mm, length 100mm, the height of record coupons cracking.
Heat resistance test；Heat resistance is laid flat according to ISO-75, sample, load 1.82Mpa.
Mortar wear test: SHT 1818-2017 plastic Ultra polyethylene mortar abrasion test method is referred to.
As a result see Table 1 for details:
The performance test results of each composite material of table 1
It can be seen that load has the carbon fiber of silicon dioxide microsphere, process from embodiment 1-5 and comparative example 1-3 test result
Silane-modified glass fibre and PCTG resin complex, can effectively improve the intensity and wear-resisting property of resin.
Claims (8)
1. a kind of wear-resisting, high-strength PC TG composite material, which is characterized in that including following parts by weight of component: PCTG resin 30~
75 parts, 15~50 parts of glass fibre, 5~15 parts of carbon fiber, 0~15 part of polytetrafluoroethylene powder, ultra-high molecular weight polyethylene 0~10
Part, 2~10 parts of molybdenum disulfide；And suitable processing aid；
It is described it is carbon fiber loaded have silicon dioxide microsphere, the glass fibre is by silane-modified.
2. wear-resisting, high-strength PC TG composite material according to claim 1, which is characterized in that further include polytetrafluoroethylene (PTFE)
0~15 part of powder, 2~10 parts of molybdenum disulfide, 0.2~1.5 part of coupling agent, 0.2~1 part of antioxidant, 0.1~0.5 part of the steady agent of light；Increase
Tough dose 3-20 parts；0.2~2 part of processing aid；
Wherein, the polytetrafluoroethylene powder molecular weight is less than 10,000, and partial size is at 0.5~15 μm；Ultra-high molecular weight polyethylene molecular weight
Greater than 1,500,000；Molybdenum disulfide is 1250 mesh.
3. wear-resisting, high-strength PC TG composite material according to claim 2, which is characterized in that the hydroxy silicon oil is viscous
Degree is 30~50mpa/s, and hydroxyl molar content is 5~10%.
4. wear-resisting, high-strength PC TG composite material according to claim 4, which is characterized in that the toughener is second
Alkene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-octene copolymerization
Object grafted maleic anhydride, ternary isopropyl grafting rubbers maleic anhydride, ethylene-vinyl acetate copolymer, styrene-hydrogenation polybutadiene
One or more of alkene-styrene block copolymer mixture.
5. wear-resisting, high-strength PC TG composite material according to claim 4, which is characterized in that the coupling agent is silane
Coupling agent, aluminate coupling agent, titanate coupling agent or zirconium ester coupling agent；The silane coupling agent is three second of 3- aminopropyl
Oxysilane, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane
One or more of mixture；Titanate coupling agent is isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl
One of dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters), isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters
Or several mixtures；Zirconium ester coupling agent is zirconium-n-propylate；Aluminate coupling agent is three isopropyl ester of aluminic acid.
6. wear-resisting, high-strength PC TG composite material according to claim 2, which is characterized in that the antioxidant be phenols,
One or more of amine, phosphorous acid esters, thioesters, matal deactivator mixture；
The phenolic antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and four [β-(3,5-
One or both of di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester；Amine antioxidants be octylated diphenylamine and
One or both of N, N '-diisooctyl p-phenylenediamine；Phosphite ester antioxidant is that three [2,4- di-tert-butyl-phenyls] are sub-
Phosphate；Thioester antioxidant is thio-2 acid double one of octadecyls and thiodipropionic acid bis-dodecanol ester or two
Kind；Matal deactivator is N, bis- salicylidene propane diamine of N'-.
7. wear-resisting, high-strength PC TG composite material according to claim 2, which is characterized in that the processing aid
Silicone powder, calcium stearate, zinc stearate, dimethicone, N, one or more of N '-ethylene bis stearamide mixture；
The steady agent of light is one or both of diformazan ketone and hindered amines mixture；The steady agent of diformazan ketone light is 2- [4-
[2- hydroxyl -3- tridecane epoxide propyl] oxygroup] -2- hydroxy phenyl] bis- (2,4- the 3,5-dimethylphenyl) -1,3,5- triazines of -4,6-
With 2- [4- [2- hydroxyl -3- dodecyloxy propyl] oxygroup] -2- hydroxy phenyl] bis- (the 2,4- 3,5-dimethylphenyls) -1,3 of -4,6-,
5- triazine mixture；The steady agent of hindered amines light is poly-succinic (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine ethanol) ester.
8. a kind of wear-resisting, high-strength PC TG composite material preparation method as claimed in claim 1, feature exist
In, comprising the following steps:
Step 1: proportionally weighing each raw material component；
Step 2: PCTG resin is 5 hours dry at 105 DEG C；
Step 3: other components will be uniformly mixed, and be placed in double screw extruder, in extruder in addition to glass fibre and carbon fiber
Glass fibre and carbon fiber is added in downstream, obtains product by melting, mixing, extrusion, cooling, drying, pelletizing；The step 3
The temperature of middle melting is 223~237 DEG C.
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| CN102876040A (en) * | 2012-10-08 | 2013-01-16 | 合肥杰事杰新材料股份有限公司 | Polyphenylene sulfide composite material and preparation method thereof |
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