CN114181522B - Alcoholysis-resistant heat-stable PPA composite material and preparation method thereof - Google Patents
Alcoholysis-resistant heat-stable PPA composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114181522B CN114181522B CN202111293040.6A CN202111293040A CN114181522B CN 114181522 B CN114181522 B CN 114181522B CN 202111293040 A CN202111293040 A CN 202111293040A CN 114181522 B CN114181522 B CN 114181522B
- Authority
- CN
- China
- Prior art keywords
- coupling agent
- hydrolysis
- alcoholysis
- ppa
- stable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 61
- 239000003365 glass fiber Substances 0.000 claims abstract description 58
- 230000007062 hydrolysis Effects 0.000 claims abstract description 58
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 58
- 239000004593 Epoxy Substances 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 14
- 239000002667 nucleating agent Substances 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920006375 polyphtalamide Polymers 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- FIASKJZPIYCESA-UHFFFAOYSA-L calcium;octacosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O FIASKJZPIYCESA-UHFFFAOYSA-L 0.000 claims description 18
- VYXPIEPOZNGSJX-UHFFFAOYSA-L zinc;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Zn+2].[O-]P([O-])(=O)C1=CC=CC=C1 VYXPIEPOZNGSJX-UHFFFAOYSA-L 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 229920000554 ionomer Polymers 0.000 claims description 12
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 11
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 claims description 11
- SIINVGJQWZKNSJ-UHFFFAOYSA-K neodymium(3+);octadecanoate Chemical compound [Nd+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SIINVGJQWZKNSJ-UHFFFAOYSA-K 0.000 claims description 11
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000413 hydrolysate Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- RWXOJQGSZWUIEJ-UHFFFAOYSA-K lanthanum(3+);octadecanoate Chemical compound [La+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O RWXOJQGSZWUIEJ-UHFFFAOYSA-K 0.000 claims description 2
- 238000000520 microinjection Methods 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- HKITTYDLDOKDRC-UHFFFAOYSA-K octadecanoate;praseodymium(3+) Chemical compound [Pr+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HKITTYDLDOKDRC-UHFFFAOYSA-K 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 229920006182 PA 6T/6I/66 Polymers 0.000 claims 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 41
- 229920001778 nylon Polymers 0.000 abstract description 9
- 239000004677 Nylon Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003878 thermal aging Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- -1 rare earth compound Chemical class 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004954 Polyphthalamide Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZKXBDPZAQUNPOY-UHFFFAOYSA-N 1-azaniumylhexylazanium;hexanedioate Chemical compound CCCCCC(N)N.OC(=O)CCCCC(O)=O ZKXBDPZAQUNPOY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical compound NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and discloses an alcoholysis-resistant heat-stable PPA composite material and a preparation method thereof. The alcoholysis-resistant heat-stable PPA composite material comprises, by weight, 60-75 parts of PPA resin, 0.5-2 parts of epoxy pre-hydrolysis coupling agent, 1-4 parts of heat stabilizer, 25-40 parts of chopped glass fiber, 0.1-0.4 part of nucleating agent, 0.4-0.8 part of antioxidant and 0.4-0.8 part of lubricant. The material provided by the invention has excellent mechanical property and processability, and can solve the problems of high water absorption, poor hydrolysis resistance, poor creep resistance, poor thermal stability, poor dimensional stability and the like of long carbon chain nylon reinforced materials used in the industries of automobiles, electric tools and electronic appliances.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an alcoholysis-resistant heat-stable PPA composite material and a preparation method thereof.
Background
The PA66 and PA6 equal-length carbon chain nylon has the characteristics of oil resistance, organic solvent resistance, excellent mechanical property and the like, and is widely applied to the fields of electronic appliances, automobiles, household appliances, office equipment and the like. However, long carbon chain nylons are prone to water absorption, poor hydrolysis resistance, poor thermal stability and poor dimensional stability, and these drawbacks limit their application in high temperature and high humidity or water environments. On the other hand, the metal material has the characteristics of high strength, corrosion resistance, stable size, creep resistance and the like, and is widely applied to the field of mechanical manufacturing. However, as the progress of industrial modernization continues to advance, the disadvantages of heavy and low cost performance of metal materials are also increasingly highlighted.
Polyphthalamide (Polyphthalamide, PPA) is a semiaromatic polyamide synthesized from terephthalic acid or phthalic acid and adipic acid hexanediamine salt as raw materials. Semi-aromatic nylon is a semi-crystalline polymer with a melting point between 290-320 ℃. Compared with common long carbon chain nylon, the nylon has the following characteristics: 1. the water absorption is low, the rigidity is good, the creep resistance is strong, and the strength is better especially kept under the high-temperature and high-humidity environment, so that the water-absorbing agent is widely applied to parts working under water; 2. the modified PPA material has good thermal stability, can work in an environment of 150 ℃ for a long time, and can be widely applied to structural parts working in a high-temperature environment; 3. the PPA material has good dimensional stability, low thermal expansion coefficient and water absorption rate, and can be widely applied to the field with high dimensional accuracy.
With the progress of the technology level in recent years, products of various industries are continuously updated. Intelligent products in industries such as automobiles, household appliances, furniture, office appliances and the like are continuously introduced. Artificial intelligence products are continually shrinking in size and integrating more components internally, meaning that the distance between internal components will be smaller and the amount of heat generated by the interior will be greater, so material updating for manufacturing the internal components is urgent. On the other hand, ecological civilization construction greatly calls for energy conservation and emission reduction, and requires that each large equipment manufacturer, especially an automobile factory, make consumption reduction targets, which greatly accelerates the progress of replacing steel with plastic in the automobile and even the whole mechanical industry. The glass fiber reinforced high-temperature nylon has the highest specific strength in engineering plastics, has excellent temperature resistance and hydrolysis resistance, is very suitable for being applied to high-temperature and high-humidity environments instead of metal materials, but the performance of the existing nylon materials needs to be improved, in particular to the performances of hydrolysis resistance, dimensional stability, thermal aging resistance and the like.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide an alcoholysis-resistant heat-stable PPA composite material and a preparation method thereof, the material provided by the invention has excellent mechanical property and processing property, can solve the problems of high water absorption, poor hydrolysis resistance, poor creep resistance, poor thermal stability, poor dimensional stability and the like of long carbon chain nylon reinforced materials used in the industries of automobiles, electric tools and electronic appliances.
In order to achieve the purpose of the invention, the alcoholysis-resistant heat-stable PPA composite material comprises the following components in parts by weight:
Further, in some embodiments of the invention, the PPA resin is one or more of a poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer (poly (hexamethylene terephthalamide), hexamethylene adipamide block copolymer), poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-hexamethylene adipamide copolymer, poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) copolymer.
Preferably, in some embodiments of the present invention, the PPA resin is a poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-hexamethylene adipamide copolymer, preferably wherein the molar ratio of the monomers copolymerized is 5:4:1; more preferably, the PPA resin has a viscosity of from 0.7 to 1.0dL/g.
Further, in some embodiments of the invention, the epoxy pre-hydrolysis coupling agent is a hydrolysate of one or more of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
Preferably, in some embodiments of the present invention, the epoxy-based pre-hydrolysis coupling agent is beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane hydrolysate.
Further, in some embodiments of the invention, the epoxy-based pre-hydrolysis coupling agent is the product of hydrolysis using a methanol, acetic acid mixture as the hydrolysis solution.
Preferably, in some embodiments of the present invention, the mass ratio of the epoxy coupling agent in the epoxy pre-hydrolysis coupling agent is 85-95%.
Preferably, in some embodiments of the present invention, the weight ratio of methanol to acetic acid in the mixture of methanol and acetic acid is 20-30:1.
Further, in some embodiments of the present invention, the preparation method of the epoxy-based pre-hydrolysis coupling agent is divided into: a. dropwise adding an epoxy coupling agent into the hydrolysis solution, and stirring; b. standing for 2-4 hr, and vacuum distilling in 60-80deg.C oven for 1-2 hr.
Preferably, in some embodiments of the invention, the time of the dropwise addition is 30-40 minutes and the stirring rate is 100-150rpm.
Further, in some embodiments of the invention, the chopped glass fibers are surface treated hydrolysis resistant alkali free chopped glass fibers having a length of 1-4mm and a diameter of 9-12 μm.
Further, in some embodiments of the invention, the heat stabilizer is one or more of polyether polyol, sorbitol, dipentaerythritol, preferably dipentaerythritol.
Further, in some embodiments of the invention, the nucleating agent is a complex formed by reacting zinc phenylphosphonate and calcium montanate in solution.
Preferably, in some embodiments of the present invention, the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1:3-5.
Further, in some embodiments of the invention, the antioxidant is a rare earth compound.
Preferably, in some embodiments of the present invention, the antioxidant is one or more of neodymium stearate, praseodymium stearate, lanthanum stearate, samarium oxide, yttrium oxide, and oxidized bait, more preferably neodymium stearate.
Preferably, in some embodiments of the present invention, the lubricant is one or more of silicone powder, ethylene bis-stearamide, pentaerythritol stearate, calcium stearate, ethylene acrylic acid ionomer, more preferably ethylene acrylic acid ionomer.
In still another aspect, the present invention further provides a method for preparing the foregoing alcoholysis-resistant thermostable PPA composite material, the method comprising the steps of:
(1) Placing PPA resin in a baking oven for baking at 110-130 ℃ for 2-4 hours, and controlling the water content below 0.1%;
(2) Weighing raw materials except for the chopped glass fibers and the epoxy pre-hydrolysis coupling agent according to the required weight parts;
(3) Uniformly mixing the raw materials weighed in the step (2) for later use;
(4) Granulating: and (3) putting the uniformly mixed raw materials into a double-screw extruder for melt extrusion, adding the chopped glass fibers through side feeding, dripping the epoxy pre-hydrolysis coupling agent from a second exhaust port of the extruder, and keeping the temperature of each temperature zone of the extruder at 290-335 ℃ to finally obtain the product.
Furthermore, the addition amount of the epoxy pre-hydrolysis coupling agent can be precisely controlled through a microinjection pump at a feed opening, and the coupling agent is contained in a heat-preserving barrel, and the temperature of the heat-preserving barrel is 60-80 ℃; the coupling agent is added in the mixing section, so that the coupling agent cannot be subjected to excessive shearing heat in the machine barrel, the chemical structure of the coupling agent is protected, the volatilization amount of the coupling agent is reduced, and the adhesive force between the components of the material is improved by carrying out chemical reaction between the matrix resin and the glass fiber surface impregnating compound and the coupling agent under the condition of melting.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the dispersibility of the nucleating agent in PPA resin is greatly improved by adding the complexed nucleating agent, so that the properties of the material in the aspects of hydrolysis resistance, dimensional stability, thermal aging and the like are greatly improved;
(2) The invention uses rare earth compound as antioxidant and polyol compound as heat stabilizer, and the two compounds have good synergistic effect. Wherein, rare earth elements can be complexed with amide groups of nylon under high temperature to prevent the material from breaking and degrading; the polyol can generate self dehydration reaction to form ether under the high temperature condition, a compact protective layer is formed on the surface of the material to prevent oxygen from entering, and the mechanical property retention rate of the manufactured PPA material after heat aging at 210 ℃ for 1000 hours is more than 60%.
(3) The composite material contains the epoxy pre-hydrolysis coupling agent, and the coupling agent after hydrolysis has stronger cohesiveness and reactivity and plays a good role of an interface binder. In addition, the epoxy pre-hydrolysis coupling agent is added in the extrusion process through a micro pump, so that the coupling agent is prevented from being degraded or volatilized by heating, and the coupling agent are subjected to chemical reaction under the condition that the matrix resin and the glass fiber surface impregnating compound are melted. Therefore, the hydrolysis resistance of the material is greatly improved from the aspects of formulation design and process improvement, and the mechanical property retention rate of the manufactured PPA material after the alcoholysis test at 130 ℃ for 1000 hours is more than 80%.
(4) The invention has the advantages of safe and environment-friendly production process, simple production process and equipment, easy realization of industrial production, low cost, suitability for large-scale popularization and good economic benefit.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is intended to be illustrative of the invention and not restrictive.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Furthermore, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., described below mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
An alcoholysis-resistant heat-stable PPA composite material comprises the following components in parts by weight:
Putting the materials except the chopped glass fibers and the epoxy pre-hydrolysis coupling agent into a high-speed mixer for mixing uniformly (mixing for 3 minutes, and the rotating speed of the high-speed mixer is 500 RPM), then putting the mixed materials into a main discharging barrel of an extruder for granulating through the extruder, adding 30 parts of chopped fibers in the extrusion process in a side feeding way, adding 0.5 part of the epoxy pre-hydrolysis coupling agent in a micro pump, keeping vacuum on, and keeping the temperature of each temperature zone of the extruder to be: one zone 150 ℃, two zones 320 ℃, three zones 320 ℃, four zones 320 ℃, five zones 310 ℃, six zones 300 ℃, seven zones 290 ℃, eight zones 290 ℃, nine zones 290 ℃, ten zones 290 ℃, eleven zones 300 ℃, a machine head 310 ℃, and an extruder speed of 400RPM.
The PPA resin is a poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-hexamethylene adipamide copolymer, wherein the molar ratio of the copolymerization of the monomers is 5:4:1; the epoxy group prehydrolysis coupling agent is beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex formed by reacting zinc phenylphosphonate and calcium montanate in a solution, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1:4, a step of; the antioxidant is neodymium stearate; the lubricant is an ethylene acrylic acid ionomer.
Example 2
This embodiment differs from embodiment 1 in that: firstly, weighing the following materials in parts by weight:
Putting the materials except the chopped glass fibers and the epoxy pre-hydrolysis coupling agent into a high-speed mixer for mixing uniformly (mixing for 3 minutes, and the rotating speed of the high-speed mixer is 500 RPM), then putting the mixed materials into a main discharging barrel of an extruder for granulating through the extruder, adding 30 parts of chopped fibers in the extrusion process in a side feeding way, adding 1 part of the epoxy pre-hydrolysis coupling agent through a micropump, and keeping vacuum on, wherein the temperature of each temperature zone of the extruder is as follows: one zone 150 ℃, two zones 320 ℃, three zones 320 ℃, four zones 320 ℃, five zones 310 ℃, six zones 300 ℃, seven zones 290 ℃, eight zones 290 ℃, nine zones 290 ℃, ten zones 290 ℃, eleven zones 300 ℃, a machine head 310 ℃, and an extruder speed of 400RPM.
The PPA resin is a poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-hexamethylene adipamide copolymer, wherein the molar ratio of the copolymerization of the monomers is 5:4:1; the epoxy group prehydrolysis coupling agent is beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex formed by reacting zinc phenylphosphonate and calcium montanate in a solution, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1:4, a step of; the antioxidant is neodymium stearate; the lubricant is an ethylene acrylic acid ionomer.
Example 3
This embodiment differs from embodiment 1 in that: firstly, weighing the following materials in parts by weight:
Putting the materials except the chopped glass fibers and the epoxy pre-hydrolysis coupling agent into a high-speed mixer for mixing uniformly (mixing for 3 minutes, and the rotating speed of the high-speed mixer is 500 RPM), then putting the mixed materials into a main discharging barrel of an extruder for granulating through the extruder, adding 40 parts of chopped fibers in the extrusion process in a side feeding way, adding 1 part of the epoxy pre-hydrolysis coupling agent through a micropump, and keeping vacuum on, wherein the temperature of each temperature zone of the extruder is as follows: one zone 150 ℃, two zones 320 ℃, three zones 320 ℃, four zones 320 ℃, five zones 310 ℃, six zones 300 ℃, seven zones 290 ℃, eight zones 290 ℃, nine zones 290 ℃, ten zones 290 ℃, eleven zones 300 ℃, a machine head 310 ℃, and an extruder speed of 400RPM.
The PPA resin is a poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-hexamethylene adipamide copolymer, wherein the molar ratio of the copolymerization of the monomers is 5:4:1; the epoxy group prehydrolysis coupling agent is beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex formed by reacting zinc phenylphosphonate and calcium montanate in a solution, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1:4, a step of; the antioxidant is neodymium stearate; the lubricant is an ethylene acrylic acid ionomer.
Comparative example 1
Comparative example 1 differs from example 1 in that: firstly, weighing the following materials in parts by weight:
Putting the materials except the chopped glass fibers and the alkyl coupling agent into a high-speed mixer for mixing uniformly (mixing for 3 minutes, wherein the rotating speed of the high-speed mixer is 500 RPM), then putting the mixed materials into a main discharging barrel of the extruder for granulating through the extruder, adding 30 parts of chopped fibers in the extrusion process in a side feeding way, adding 0.5 part of the alkyl coupling agent in a micro-pump injection way, keeping vacuum on, and keeping the temperature of each temperature zone of the extruder to be: one zone 150 ℃, two zones 320 ℃, three zones 320 ℃, four zones 320 ℃, five zones 310 ℃, six zones 300 ℃, seven zones 290 ℃, eight zones 290 ℃, nine zones 290 ℃, ten zones 290 ℃, eleven zones 300 ℃, a machine head 310 ℃, and an extruder speed of 400RPM.
The PPA resin is a poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-hexamethylene adipamide copolymer, wherein the molar ratio of the copolymerization of the monomers is 5:4:1; the alkyl coupling agent is octaalkyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex formed by reacting zinc phenylphosphonate and calcium montanate in a solution, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1:4, a step of; the antioxidant is neodymium stearate; the lubricant is an ethylene acrylic acid ionomer.
Comparative example 2
Comparative example 2 differs from example 1 in that: firstly, weighing the following materials in parts by weight:
Putting the materials except the chopped glass fibers and the epoxy pre-hydrolysis coupling agent into a high-speed mixer for mixing uniformly (mixing for 3 minutes, and the rotating speed of the high-speed mixer is 500 RPM), then putting the mixed materials into a main discharging barrel of an extruder for granulating through the extruder, adding 30 parts of chopped fibers in the extrusion process in a side feeding way, adding 0.5 part of the epoxy pre-hydrolysis coupling agent in a micro pump injection way, keeping vacuum on, and keeping the temperature of each temperature zone of the extruder to be: one 150 ℃, two 320 ℃, three 320 ℃, four 320 ℃, five 310 ℃, six 300 ℃, seven 290 ℃, eight 290 ℃, nine 290 ℃, ten 290 ℃, eleven 300 ℃ and a handpiece 310 ℃. The extruder speed was 400RPM.
The PPA resin is a poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-hexamethylene adipamide copolymer, wherein the molar ratio of the copolymerization of the monomers is 5:4:1; the epoxy group prehydrolysis coupling agent is beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the nucleating agent is a complex formed by reacting zinc phenylphosphonate and calcium montanate in a solution, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1:4, a step of; the antioxidant is neodymium stearate; the lubricant is an ethylene acrylic acid ionomer.
Comparative example 3
Comparative example 3 differs from example 1 in that: firstly, weighing the following materials in parts by weight:
Putting the materials except the chopped glass fibers and the epoxy pre-hydrolysis coupling agent into a high-speed mixer for mixing uniformly (mixing for 3 minutes, and the rotating speed of the high-speed mixer is 500 RPM), then putting the mixed materials into a main discharging barrel of an extruder for granulating through the extruder, adding 30 parts of chopped fibers in the extrusion process in a side feeding way, adding 0.5 part of the epoxy pre-hydrolysis coupling agent in a micro pump injection way, keeping vacuum on, and keeping the temperature of each temperature zone of the extruder to be: one 150 ℃, two 320 ℃, three 320 ℃, four 320 ℃, five 310 ℃, six 300 ℃, seven 290 ℃, eight 290 ℃, nine 290 ℃, ten 290 ℃, eleven 300 ℃ and a handpiece 310 ℃. The extruder speed was 400RPM.
The PPA resin is a poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-hexamethylene adipamide copolymer, wherein the molar ratio of the copolymerization of the monomers is 5:4:1; the epoxy group prehydrolysis coupling agent is beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex formed by reacting zinc phenylphosphonate and calcium montanate in a solution, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1:4, a step of; the lubricant is an ethylene acrylic acid ionomer.
Comparative example 4
Comparative example 4 differs from example 1 in that: firstly, weighing the following materials in parts by weight:
Putting the materials except the chopped glass fibers and the epoxy pre-hydrolysis coupling agent into a high-speed mixer for mixing uniformly (mixing for 3 minutes, and the rotating speed of the high-speed mixer is 500 RPM), then putting the mixed materials into a main discharging barrel of an extruder for granulating through the extruder, adding 30 parts of chopped fibers in the extrusion process in a side feeding way, adding 0.5 part of the epoxy pre-hydrolysis coupling agent in a micro pump injection way, keeping vacuum on, and keeping the temperature of each temperature zone of the extruder to be: one 150 ℃, two 320 ℃, three 320 ℃, four 320 ℃, five 310 ℃, six 300 ℃, seven 290 ℃, eight 290 ℃, nine 290 ℃, ten 290 ℃, eleven 300 ℃ and a handpiece 310 ℃. The extruder speed was 400RPM.
The PPA resin is a poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-hexamethylene adipamide copolymer, wherein the molar ratio of the copolymerization of the monomers is 5:4:1; the epoxy group prehydrolysis coupling agent is beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the antioxidant is neodymium stearate; the lubricant is an ethylene acrylic acid ionomer.
Comparative example 5
Comparative example 5 differs from example 1 in that: firstly, weighing the following materials in parts by weight:
Putting the materials except the chopped glass fibers into a high-speed mixer for mixing uniformly (mixing for 3 minutes, wherein the rotating speed of the high-speed mixer is 500 RPM), then putting the mixed materials into a main discharging barrel of an extruder for granulating through the extruder, adding 30 parts of chopped fibers in the extrusion process in a side feeding manner, keeping vacuum open, and keeping the temperature of each temperature zone of the extruder to be: one 150 ℃, two 320 ℃, three 320 ℃, four 320 ℃, five 310 ℃, six 300 ℃, seven 290 ℃, eight 290 ℃, nine 290 ℃, ten 290 ℃, eleven 300 ℃ and a handpiece 310 ℃. The extruder speed was 400RPM.
The PPA resin is a poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-hexamethylene adipamide copolymer, wherein the molar ratio of the copolymerization of the monomers is 5:4:1; the epoxy group prehydrolysis coupling agent is beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex formed by reacting zinc phenylphosphonate and calcium montanate in a solution, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1:4, a step of; the antioxidant is neodymium stearate; the lubricant is an ethylene acrylic acid ionomer.
Table 1 test data for examples 1-3 and comparative examples 1-5
Note that: the alcoholysis solution is glycol and water, the mass ratio of the glycol to the water is 1:1, and the alcoholysis is carried out for 1000 hours at 130 ℃; the heat aging conditions were 210℃for 1000 hours.
It can be seen from the table that the alcoholysis resistance and the thermal aging resistance of the material are improved with the addition of the epoxy pre-hydrolysis coupling agent, the heat stabilizer, the antioxidant and the nucleating agent and by changing the addition mode of the coupling agent. Under the condition that the consumption of the coupling agent is unchanged, the alcoholysis resistance and the thermal aging resistance of the material are improved along with the increase of the content of the glass fiber.
It will be readily appreciated by those skilled in the art that the foregoing is merely illustrative of the present invention and is not intended to limit the invention, but any modifications, equivalents, improvements or the like which fall within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The alcoholysis-resistant heat-stable PPA composite is characterized by comprising the following components in parts by weight:
60-75 parts of PPA resin;
0.5-2 parts of epoxy pre-hydrolysis coupling agent;
25-40 parts of chopped glass fibers;
1-4 parts of a heat stabilizer;
0.1-0.4 part of nucleating agent;
0.4-0.8 part of antioxidant;
0.4-0.8 parts of lubricant;
the PPA resin is a poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-poly (hexamethylene adipamide) copolymer;
The mole ratio of each unit copolymerization in the poly (hexamethylene terephthalamide) -co-poly (hexamethylene isophthalamide) -co-poly (hexamethylene adipamide) copolymer is 5:4:1;
The epoxy pre-hydrolysis coupling agent is a hydrolysate of one or more of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3- (2, 3-epoxypropoxy) propyl methyl diethoxy silane and beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane;
The epoxy pre-hydrolysis coupling agent is a product of hydrolysis by using a mixture of methanol and acetic acid as a hydrolysis solution; the mass ratio of the epoxy coupling agent in the epoxy pre-hydrolysis coupling agent is 85-95%; the weight ratio of the methanol to the acetic acid in the mixture of the methanol and the acetic acid is 20-30:1, a step of;
the preparation method of the epoxy group prehydrolysis coupling agent comprises the following steps: a. dropwise adding an epoxy coupling agent into the hydrolysis solution, and stirring; b. standing for 2-4 hours, then placing into a 60-80 ℃ oven for reduced pressure distillation for 1-2 hours, and taking out; the dripping time is 30-40 minutes, and the stirring speed is 100-150rpm;
The nucleating agent is a complex formed by reacting zinc phenylphosphonate and calcium montanate in a solution; the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1:3-5;
the heat stabilizer is one or more of polyether polyol, sorbitol and dipentaerythritol;
The antioxidant is one or more of neodymium stearate, praseodymium stearate and lanthanum stearate;
the preparation method of the alcoholysis-resistant heat-stable PPA composite material comprises the following steps:
(1) Placing PPA resin in a baking oven for baking at 110-130 ℃ for 2-4 hours, and controlling the water content below 0.1%;
(2) Weighing raw materials except for the chopped glass fibers and the epoxy pre-hydrolysis coupling agent according to the required weight parts;
(3) Uniformly mixing the raw materials weighed in the step (2) for later use;
(4) Granulating: and (3) putting the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the chopped glass fibers are added through side feeding, the epoxy pre-hydrolysis coupling agent is dripped from a second exhaust port of the extruder, and the temperature of each temperature zone of the extruder is kept at 290-335 ℃, so that the product is finally obtained.
2. The alcoholysis-resistant heat-stable PPA composite according to claim 1, wherein the PPA resin has an intrinsic viscosity of 0.7-1.0dL/g.
3. The alcoholysis-resistant heat-stable PPA composite according to claim 1, wherein the epoxy-based pre-hydrolysis coupling agent is a beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane hydrolysate.
4. The alcoholysis-resistant heat-stable PPA composite according to claim 1, wherein the chopped glass fibers are surface-treated hydrolysis-resistant alkali-free chopped glass fibers, the length of the chopped glass fibers is 1-4mm, and the diameter of the chopped glass fibers is 9-12 μm.
5. The alcoholysis-resistant heat-stable PPA composite of claim 4, wherein the heat stabilizer is dipentaerythritol.
6. The alcoholysis-resistant heat-stable PPA composite material according to claim 1, wherein the antioxidant is neodymium stearate.
7. The alcoholysis-resistant heat-stable PPA composite according to claim 1, wherein the lubricant is one or more of silicone powder, ethylene bis stearamide, pentaerythritol stearate, calcium stearate, ethylene acrylic acid ionomer.
8. The alcoholysis-resistant heat stable PPA composite according to claim 1, wherein the lubricant is an ethylene-acrylic acid ionomer.
9. The method for preparing the alcoholysis-resistant heat-stable PPA composite material according to any one of claims 1 to 8, comprising the steps of:
(1) Placing PPA resin in a baking oven for baking at 110-130 ℃ for 2-4 hours, and controlling the water content below 0.1%;
(2) Weighing raw materials except for the chopped glass fibers and the epoxy pre-hydrolysis coupling agent according to the required weight parts;
(3) Uniformly mixing the raw materials weighed in the step (2) for later use;
(4) Granulating: and (3) putting the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the chopped glass fibers are added through side feeding, the epoxy pre-hydrolysis coupling agent is dripped from a second exhaust port of the extruder, and the temperature of each temperature zone of the extruder is kept at 290-335 ℃, so that the product is finally obtained.
10. The preparation method of the alcoholysis-resistant heat-stable PPA composite material according to claim 9, wherein the addition amount of the epoxy pre-hydrolysis coupling agent is precisely controlled by a microinjection pump at a feed opening, and the coupling agent is contained in a heat-preserving barrel, and the temperature of the heat-preserving barrel is 60-80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111293040.6A CN114181522B (en) | 2021-11-03 | 2021-11-03 | Alcoholysis-resistant heat-stable PPA composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111293040.6A CN114181522B (en) | 2021-11-03 | 2021-11-03 | Alcoholysis-resistant heat-stable PPA composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114181522A CN114181522A (en) | 2022-03-15 |
| CN114181522B true CN114181522B (en) | 2024-08-09 |
Family
ID=80540612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111293040.6A Active CN114181522B (en) | 2021-11-03 | 2021-11-03 | Alcoholysis-resistant heat-stable PPA composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114181522B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112525A (en) * | 2008-07-30 | 2011-06-29 | 纳幕尔杜邦公司 | Heat resistant molded or extruded thermoplastic articles |
| CN102634189A (en) * | 2011-02-15 | 2012-08-15 | 汉达精密电子(昆山)有限公司 | PPA (polyphthalamide) reinforced material and preparation method thereof |
| CN107227021A (en) * | 2017-04-26 | 2017-10-03 | 德力西电气有限公司 | Glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material and preparation method thereof |
| CN111234314A (en) * | 2020-04-01 | 2020-06-05 | 山西省化工研究所（有限公司） | Complex nucleating agent for polyester and preparation method thereof |
| CN111423468A (en) * | 2020-04-01 | 2020-07-17 | 山西省化工研究所（有限公司） | Complex type polyester nucleating agent, compound containing polyester nucleating agent and preparation method |
| CN112724670A (en) * | 2020-12-29 | 2021-04-30 | 上海普利特复合材料股份有限公司 | High-strength and high-heat-resistance bio-based polyamide composition and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292805A (en) * | 1992-05-29 | 1994-03-08 | Amoco Corporation | Filled polyphthalamide blends having improved processability and composite and filled articles therefrom |
| KR100844728B1 (en) * | 2006-12-12 | 2008-07-07 | 현대자동차주식회사 | Polyamide Resin Composition for Automobile Radiator |
| KR100931151B1 (en) * | 2007-12-13 | 2009-12-10 | 현대자동차주식회사 | Polyamide resin composition |
| KR101071768B1 (en) * | 2009-11-18 | 2011-10-11 | 현대자동차주식회사 | Resin composition for vehicle thermostat housing |
| CN102311638B (en) * | 2010-12-21 | 2012-12-19 | 深圳市科聚新材料有限公司 | Hydrolysis-resistance alcoholysis-resistance glass fiber reinforced PPA (phenyl-propanolamine) material and preparation method thereof |
| WO2013033287A2 (en) * | 2011-08-31 | 2013-03-07 | Invista Technologies S.A R.L. | Compositions of polyhydric alcohols and polyamides |
| CN105017763A (en) * | 2014-04-21 | 2015-11-04 | 上海杰事杰新材料(集团)股份有限公司 | Rare earth modified glass fiber-reinforced high temperature-resistant nylon composite material and preparation method thereof |
| CN104292825A (en) * | 2014-07-08 | 2015-01-21 | 东莞市众一新材料科技有限有限公司 | A flame-retardant reinforced high-temperature nylon composite material and its preparation method |
| CN107236293A (en) * | 2017-04-26 | 2017-10-10 | 木林森股份有限公司 | Modified PPA composite material and preparation method and application thereof |
| JP2020033548A (en) * | 2018-08-23 | 2020-03-05 | ユニチカ株式会社 | Semi-aromatic polyamide resin composition and molded article obtained by molding the same |
| CN112574557B (en) * | 2020-11-27 | 2022-07-12 | 珠海万通特种工程塑料有限公司 | A kind of semi-aromatic polyamide composition and its preparation method and application |
-
2021
- 2021-11-03 CN CN202111293040.6A patent/CN114181522B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112525A (en) * | 2008-07-30 | 2011-06-29 | 纳幕尔杜邦公司 | Heat resistant molded or extruded thermoplastic articles |
| CN102634189A (en) * | 2011-02-15 | 2012-08-15 | 汉达精密电子(昆山)有限公司 | PPA (polyphthalamide) reinforced material and preparation method thereof |
| CN107227021A (en) * | 2017-04-26 | 2017-10-03 | 德力西电气有限公司 | Glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material and preparation method thereof |
| CN111234314A (en) * | 2020-04-01 | 2020-06-05 | 山西省化工研究所（有限公司） | Complex nucleating agent for polyester and preparation method thereof |
| CN111423468A (en) * | 2020-04-01 | 2020-07-17 | 山西省化工研究所（有限公司） | Complex type polyester nucleating agent, compound containing polyester nucleating agent and preparation method |
| CN112724670A (en) * | 2020-12-29 | 2021-04-30 | 上海普利特复合材料股份有限公司 | High-strength and high-heat-resistance bio-based polyamide composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114181522A (en) | 2022-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113025035B (en) | Laser-markable halogen-free flame-retardant nylon composite material and preparation method thereof | |
| KR100436618B1 (en) | A polyamide resin composition and moldings thereof | |
| EP1266930A1 (en) | Polyamide composition | |
| CN103232685A (en) | Low-mold-deposit high-surface-quality high-content glass fiber reinforced material and preparation method thereof | |
| CN111393819A (en) | High-fluidity, heat-resistant and corrosion-resistant polyester alloy composite material and preparation method and application thereof | |
| CN101910305A (en) | Mobile terminal part | |
| CN105837803A (en) | Liquid crystal polyester and its molded composition and use | |
| CN107849228B (en) | Polybutylene terephthalate composition with improved hydrolytic stability | |
| CN101633774A (en) | PBT molding composite and preparation method thereof | |
| CN112194893B (en) | Hydrolysis-resistant reinforced flame-retardant PA6-POK alloy material and preparation method thereof | |
| CN114181522B (en) | Alcoholysis-resistant heat-stable PPA composite material and preparation method thereof | |
| KR20150024824A (en) | Molding material, molded body of same, and method for producing molded body | |
| CN104356589A (en) | Carbon fiber reinforced friction-resistant polyoxymethylene (POM) composite material and preparation method thereof | |
| CN109722022B (en) | Extrusion and blow molding grade glass fiber reinforced nylon material and preparation method thereof | |
| KR100853438B1 (en) | A polyamide resin composition having high heat resistance, high rigidity and excellent appearance | |
| CN114196011B (en) | Long-acting antibacterial bio-based nylon resin and preparation method thereof | |
| CN105153631B (en) | A kind of coating modified fibre reinforced ABS resin composite material and preparation method | |
| CN113736229A (en) | PBT/PC composition with high post-shrinkage rate and preparation method and application thereof | |
| CN108219389A (en) | Macromolecular coupling agent is modified fiber glass reinforced PBT composite material and preparation method thereof | |
| CN115975367B (en) | Polycarbonate composition with good processing stability, and preparation method and application thereof | |
| CN109575562B (en) | Stain-resistant PC/ABS alloy and preparation method thereof | |
| CN109796740A (en) | A kind of resistant PC/PET alloy and preparation method thereof | |
| CN109181292A (en) | A kind of glass fiber reinforced PA66 high-speed railway rail baseplate material and preparation method thereof | |
| CN104017325A (en) | Polyaryletherketone borate-modified aluminum borate crystal whisker reinforced polyether-ether-ketone composite material and preparation method thereof | |
| CN112662141A (en) | Preparation method of flame-retardant hydrolysis-resistant PBT material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |