CN112029264B - High-rigidity long-chain nylon composite material and preparation method thereof - Google Patents
High-rigidity long-chain nylon composite material and preparation method thereof Download PDFInfo
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- CN112029264B CN112029264B CN202010955677.6A CN202010955677A CN112029264B CN 112029264 B CN112029264 B CN 112029264B CN 202010955677 A CN202010955677 A CN 202010955677A CN 112029264 B CN112029264 B CN 112029264B
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- 229920001778 nylon Polymers 0.000 title claims abstract description 78
- 239000004677 Nylon Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000003365 glass fiber Substances 0.000 claims abstract description 56
- 239000007822 coupling agent Substances 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract 2
- 239000000178 monomer Substances 0.000 claims description 51
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000413 hydrolysate Substances 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 6
- -1 aliphatic diamine Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000003951 lactams Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000861 blow drying Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-amino-decanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 claims description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [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
- 238000000265 homogenisation Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000011256 inorganic filler Substances 0.000 abstract description 4
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 4
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 239000011147 inorganic material Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000000889 atomisation Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920000962 poly(amidoamine) Polymers 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- SVUJNSGGPUCLQZ-FQQAACOVSA-N tenofovir alafenamide fumarate Chemical compound OC(=O)\C=C\C(O)=O.O([P@@](=O)(CO[C@H](C)CN1C2=NC=NC(N)=C2N=C1)N[C@@H](C)C(=O)OC(C)C)C1=CC=CC=C1.O([P@@](=O)(CO[C@H](C)CN1C2=NC=NC(N)=C2N=C1)N[C@@H](C)C(=O)OC(C)C)C1=CC=CC=C1 SVUJNSGGPUCLQZ-FQQAACOVSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
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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
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Polymers & Plastics (AREA)
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- Proteomics, Peptides & Aminoacids (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a high-rigidity long-carbon-chain copolymerized nylon composite material. The high-rigidity long-chain nylon composite material is prepared from the following components: long carbon chain copolymerized nylon substrate: 30-50%, glass fiber: 50-70%, coupling agent: 1-4% and other auxiliary agents: 1 to 4 percent. The polymer base material capable of better coating the inorganic filler is obtained by self-synthesizing long carbon chain copolymerized nylon, the contact area of the inorganic material and the organic resin base body is increased by optimizing the special-shaped glass fiber, the rigidity of the composite material is further improved, meanwhile, the glass fiber is pretreated by a self-synthesizing coupling agent, the structural particularity of the coupling agent enables the nylon base material and the glass fiber interface to be more fully linked, the compatibility is improved, the bonding force of the resin base body and the glass fiber is further enhanced, and the cohesive energy of the material is increased, so that the rigidity of the composite material is greatly improved.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a high-rigidity long-chain nylon composite material and a preparation method thereof.
Background
The nylon has certain excellent characteristics, but in the application process, a pure nylon material cannot meet the requirements in many cases, such as high moisture absorption, poor product dimensional stability, and insufficient strength and hardness. The above disadvantages are compensated by adding a certain amount of glass fibers to the material. Among the disadvantages, strength and rigidity are more desirable, and glass fiber has high cost performance, not only has the characteristics of dimensional stability, corrosion resistance, heat resistance, processability resistance and easy processing, but also has great advantage in price, so that glass fiber reinforced nylon also has a "high cost performance" dazzling light ring.
Common coupling agents of the glass fiber reinforced nylon comprise a carbonate coupling agent and a silane coupling agent, and the titanate coupling agent is easy to hydrolyze in water to generate a large amount of micro bubbles, so that the titanate coupling agent cannot be well combined with the fiber, and the silane coupling agent is easier to adopt for the glass fiber reinforced nylon. It contains a chemical functional group which can form covalent bond with silanol group on the surface of glass fiber or other molecules on the surface of inorganic filler; in addition, the coupling agent has another distinct functional group bonded to the polymeric molecule to achieve good interfacial bonding, which serves to form an interconnected "bridge" between the glass fibers and the nylon resin, which fuses the two together.
It is known that under the same modification method in the past, the chemical resistance, low hygroscopicity, dimensional stability and toughness of the composite material produced by using the long carbon chain nylon are better than those of the conventional nylon, and the long carbon chain nylon has low hygroscopicity and excellent dielectric property in a humid environment, which is a characteristic that the short carbon chain nylon such as nylon 6 and nylon 66 does not have, but the rigidity is inherently weaker than other nylons such as PA66, and the like, so that the demand for improving the rigidity of the long carbon chain nylon composite material through technical means is increasingly increased. Meanwhile, long-chain nylon resins such as PA612, PA1212, PA11, and PA12 available on the market are also expensive.
In view of the above, the invention provides a high-rigidity long-chain nylon composite material and a preparation method thereof. The nylon composite material is mainly developed for the materials of the quick connector for the automobile pipeline, but is not limited to the materials, and has the advantages of chemical resistance, high rigidity, low moisture absorption, stable size and good toughness.
Disclosure of Invention
The invention provides a high-rigidity long-chain nylon composite material and a preparation method thereof. The nylon composite material is mainly developed for the materials of the quick connector for the automobile pipeline, but is not limited to the materials, and has the advantages of chemical resistance, high rigidity, low moisture absorption, stable size and good toughness.
The present invention provides the following scheme:
a high-rigidity long-chain nylon composite material is prepared from the following components in percentage by weight:
long carbon chain nylon base material: 30-50%;
glass fiber: 50-70%;
coupling agent: 1 to 4 percent;
other auxiliary agents: 1 to 4 percent.
Preferably, the content of each component is as follows:
long carbon chain nylon base material: 35 to 45 percent;
glass fiber: 55-65 percent;
coupling agent: 1 to 2 percent;
other auxiliary agents: 1 to 3 percent.
The glass fiber is selected from one or more of Taishan mountain glass fiber company T4355, chongqing International composite materials corporation ECS301HP-3-M4 and Chongqing International composite materials corporation ECS301 HP-3-H/TM.
Preferably, the other auxiliary agent comprises an antioxidant and a lubricant.
The antioxidant is selected from 1098, 168 or a mixture thereof.
The lubricant is selected from calcium stearate, TAF or mixtures thereof.
Preferably, the long carbon chain copolymerized nylon is synthesized by the following method:
(1) The following monomers were prepared:
monomer A: an amino acid or a lactam;
a monomer B: an aliphatic diamine;
a monomer C: an aliphatic dibasic acid;
(2) Salifying reaction, and condensing the monomer B and the monomer C according to the molar ratio of 1:1 to obtain an intermediate product D:
(3) Polymerization reaction: and (3) polycondensing the product D and the monomer A to obtain the long carbon chain copolymerized nylon.
Preferably, the step (2) in the synthesis method of the long carbon chain copolymerized nylon is: dissolving the monomer B and the monomer C with the same molar weight in water under the protection of nitrogen, heating to 70-80 ℃, reacting for 2 hours until the reaction solution becomes a clear solution, then adding acetone into the solution, precipitating and filtering the reaction product, washing the obtained filtrate with acetone, filtering, and drying for 24 hours at 58 ℃ to obtain a product D;
preferably, the step (3) is to input the product D and the monomer A as well as deionized water or distilled water into an automatic control polymerization kettle with a stirrer, start stirring and continuously raise the temperature when the temperature in the polymerization kettle is heated to 125 ℃, and start exhausting when the temperature reaches 140 ℃ and the air pressure is increased to 6 bar; and in the process of exhausting, the temperature in the polymerization kettle is raised to 240-320 ℃, then the water in the reaction is removed under the driving of nitrogen, after the water is removed, the copolymerized nylon melt generated in the polymerization kettle is discharged under pressure, the copolymerized nylon melt is cast and formed through a die head, and finally the copolymerized nylon is obtained through cooling and grain cutting.
Preferably, the mass content of the monomer A in the long carbon chain copolymerized nylon is 5-65%, and the mass content of the intermediate product D is 35-95%.
Preferably, in the preparation method of the long carbon chain copolymerized nylon, the amino acid or the lactam is one or a mixture of two of 10-amino n-decanoic acid, 11-amino undecanoic acid and dodecyl lactam.
The preparation method of the long carbon chain copolymerized nylon is characterized in that the aliphatic diamine is one or a mixture of hexamethylene diamine and decamethylene diamine.
The preparation method of the long carbon chain copolymerized nylon is characterized in that the aliphatic dibasic acid is one or a mixture of sebacic acid and dodecanedioic acid.
Preferably, the coupling agent used in the present invention is a dendritic silane-polyamidoamine polymer having the structure:
wherein, the end functional groups R of the finished product are two of R1 and R2, and the number ratio of R1 to R2 is 1:2-2: 1.
Preferably, the dendritic silane-polyamidoamine polymer is formed by polycondensation of the following components:
monomer A: ethylene diamine tetraacetic acid;
a monomer B:3- (2-aminoethyl- (2-carboxyethyl) amino) propionic acid;
a monomer C: ethylene diamine;
a monomer D: gamma-aminopropyltriethoxysilane.
Preferably, the dendritic silane-polyamidoamine polymer is prepared by the following method:
and condensing the monomer A and the monomer B to obtain an intermediate product E, and condensing the intermediate product E with the monomer and the monomer D again to obtain the dendritic silane-polyamide-amine polymer.
Preferably, the preparation method of the dendritic silane-polyamide-amine polymer comprises the following steps:
a first reaction stage: under the protection of nitrogen, adding the monomer A and the monomer B into an automatic control polymerization kettle with a stirrer according to the molar ratio of 1: 2-1: 8, heating to 70-95 ℃, and reacting for 2-4 hours until the reaction liquid becomes clear and bubble-free uniform liquid, thus obtaining an intermediate product E;
a second reaction stage: on the basis of the intermediate product E contained in the first reaction section, adding a monomer C into the automatic control polymerization kettle with the stirrer according to the molar ratio of the monomer C to the monomer A in the first reaction section of 2: 1-8: 1, simultaneously adding a monomer D into the automatic control polymerization kettle with the stirrer according to the molar ratio of the monomer D to the monomer A in the first reaction section of 2: 1-8: 1, starting stirring and continuously heating when the temperature in the polymerization kettle is heated to 110-125 ℃, and starting exhausting when the air pressure is increased to 5-6bar when the temperature reaches 135-150 ℃; and (3) raising the temperature in the polymerization kettle to 220-280 ℃ in the exhausting process, then removing moisture in the reaction under the driving of nitrogen, and pressurizing and discharging the generated dendritic silane-polyamide-amine polymer liquid in the polymerization kettle after the water removal is finished, wherein the dendritic silane-polyamide-amine polymer liquid is directly discharged through a die head.
The invention also provides a preparation method of the high-rigidity long-chain copolymerized nylon composite material, which is characterized by comprising the following steps:
step A: diluting the dendritic silane-polyamide-amine polymer with distilled water to obtain a coupling agent hydrolysate; and B: b, treating the glass fiber by using the coupling agent hydrolysate obtained in the step A;
and C: adding the long carbon chain copolymerized nylon resin, the lubricant and the antioxidant into a high-speed batching mixer, and mixing to obtain a pre-mixed mixture;
step D: and D, melting and extruding the premixed mixture obtained in the step C and the glass fiber pretreated by the coupling agent through a TE-75 parallel double-screw extruder, and performing water cooling, blow drying, grain cutting, homogenization and drying after extrusion to obtain the long carbon chain copolymerized nylon composite material.
Preferably, in the step D, the premixed mixture is added by a main feeder, the coupling agent pretreated glass fibers are added by a side feeder, the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone, the seventh zone, the eighth zone and the ninth zone of the extruder are sequentially set to 260 ℃, 280 ℃, 270 ℃, 260 ℃, 250 ℃, 220 ℃, 210 ℃ and 270 ℃, the temperature control error control range is +/-30 ℃, the rotating speed is set to 250r/min, and the rotating speed error control range is +/-50 r/min.
Preferably, the glass fiber is pretreated by a pretreatment apparatus as shown in FIG. 1.
Preferably, the glass fiber pretreatment comprises the steps of:
1) Adding glass fiber into a feeder with weightlessness scale metering control, and adding coupling agent hydrolysate into an atomization spraying device with weightlessness scale metering control;
2) The glass fiber enters the conveyer belt with the vibration function at the appointed feeding speed, uniformly advances along with the vibration conveyer belt and continuously turns over up and down along with the vibration, and the uniform infiltration of the coupling agent hydrolysate to the glass fiber is completed through the atomization spraying device at the appointed spraying speed. In the process, the actual addition amount of the coupling agent can be controlled by controlling the dilution degree of the coupling agent, the feeding rate of the glass fiber, the advancing rate of the vibrating conveyer belt and the spraying rate of the atomizing and spraying device to be matched with each other;
3) And (3) putting the uniformly sprayed and soaked glass fibers into a large-scale oven for heat treatment by using a tray, and finishing the process to obtain the coupling agent pretreated glass fibers.
The invention also provides application of the nylon composite material in pipeline quick connectors for automobiles.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
compared with the prior art, the polymer base material capable of better coating the inorganic filler is obtained by self-synthesizing long carbon chain copolymerized nylon, the contact area of the inorganic material and an organic resin matrix is increased by optimizing the special-shaped glass fiber, the rigidity of the composite material is further improved, meanwhile, the glass fiber is pretreated by a self-synthesizing coupling agent, the nylon base material and a glass fiber interface can be more fully linked due to the structural specificity of the coupling agent, the compatibility is improved, the bonding force of the resin matrix and the glass fiber is further enhanced, and the cohesive energy of the material is increased, so that the rigidity of the composite material is greatly improved.
Drawings
FIG. 1A glass fiber coating apparatus according to the present invention
FIG. 2 is a flow chart of the preparation of the long-chain nylon composite material of the present invention
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all the embodiments. The components of the embodiments of the present application, generally described and illustrated in the figures herein, can be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present application, as presented in the figures, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present application without making any creative effort, shall fall within the protection scope of the present application.
In the description of the embodiments of the present application, it should be noted that the terms "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings or orientations or positional relationships that are conventionally placed when the products of the present invention are used, and are used for convenience of description and simplicity of description only, and do not indicate or imply that the devices or elements that are referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present application. Moreover, the terms "first," "second," "third," and the like are used solely to distinguish one from another without necessarily indicating or implying relative importance.
Preparative example 1 (preparation of long carbon chain copolymerized nylon):
the preparation method of the long carbon chain copolymerized nylon comprises the following steps:
salt forming reaction: under the protection of nitrogen, 344kg of monomer B decamethylene diamine and 460kg of monomer C dodecanedioic acid are dissolved in water, the temperature is raised to 70-80 ℃, the reaction is carried out for 2 hours until the reaction liquid becomes clear solution, then acetone is added into the solution, the reaction product is precipitated and filtered, the obtained filtrate is washed by acetone and filtered, and then the filtrate is dried for 24 hours at 58 ℃, so that a product D is obtained;
polymerization reaction: inputting 800kg of the product D and 200kg of the monomer A together with deionized water or distilled water into an automatic control polymerization kettle with a stirrer, starting stirring and continuously heating when the temperature in the polymerization kettle is heated to 125 ℃, and exhausting when the temperature reaches 140 ℃ and the air pressure is increased to 6 bar; and (3) raising the temperature in the polymerization kettle to 255 ℃ in the exhausting process, then removing moisture in the reaction under the driving of nitrogen, pressurizing and discharging long carbon chain copolymerized nylon melt generated in the polymerization kettle after the water is discharged, casting and molding the long carbon chain copolymerized nylon melt through a die head, and finally cooling and dicing to obtain the copolymerized nylon.
The viscosity of the obtained long carbon chain copolymerized nylon resin is 2.4 measured by a Ubbelohde viscometer method.
Preparative example 2 (preparation of the dendritic silane-polyamidoamine polymer used according to the invention):
(1) Under the protection of nitrogen, 5.16kg of monomer A ethylene diamine tetraacetic acid and 8.16kg of monomer B3- (2-aminoethyl- (2-carboxyethyl) amino) propionic acid (the molar ratio of the monomer A to the monomer B is 1) are added into an automatic control polymerization kettle with a stirrer, the temperature is increased to 90 ℃, and the reaction is carried out for 3 hours until the reaction liquid becomes clear and bubble-free uniform liquid, thus obtaining an intermediate product E;
(2) Adding 2.4kg of monomer C ethylenediamine (the molar ratio of the monomer C ethylenediamine to the monomer A in the step (1) is 4: 1) and 8.84kg of monomer D gamma-aminopropyltriethoxysilane (the molar ratio of the monomer D gamma-aminopropyltriethoxysilane to the monomer A in the step (1) into the automatic control polymerization kettle with a stirrer, which contains the intermediate product E in the step (1), starting stirring and continuously heating when the temperature in the polymerization kettle is heated to 120 ℃, and starting exhausting when the temperature reaches 145 ℃ and the air pressure is increased to 5.5 bar; and (3) raising the temperature in the polymerization kettle to 270 ℃ in the exhausting process, then removing water in the reaction under the driving of nitrogen, and after the water removal is finished, pressurizing and discharging the generated dendritic silane-polyamide-amine polymer liquid in the polymerization kettle, wherein the dendritic silane-polyamide-amine polymer liquid is directly discharged through a die head.
Application example 1 and comparative examples 1-2:
the dendritic silane-polyamide-amine polymer prepared by the invention is used as a coupling agent, and is combined with the long carbon chain copolymerized nylon and glass fiber prepared by the invention, an antioxidant, a lubricant and the like to prepare a composite material, and the performance of the composite material is tested.
The raw materials were fed according to the feed ratio of each raw material in application example 1 and comparative examples 1-2 in table 1, and the preparation method was as follows:
step A: diluting and hydrolyzing the dendritic silane-polyamide-amine polymer in advance by using distilled water with the mass of 50% of that of the dendritic silane-polyamide-amine polymer for 2 hours to obtain a coupling agent hydrolysate;
and B: glass fiber is pretreated, and a pretreatment device is shown in figure 1.
1) Adding glass fiber into a feeder with weightlessness scale metering control, and adding the coupling agent hydrolysate into an atomization spraying device with weightlessness scale metering control;
2) The glass fiber enters the conveyer belt with the vibration function at the specified feeding speed, uniformly advances along with the vibration of the conveyer belt and continuously turns over up and down along with the vibration, and the uniform infiltration of the coupling agent hydrolysate on the glass fiber is completed through the atomization spraying device at the specified spraying speed. In the process, the actual addition amount of the coupling agent can be controlled by controlling the dilution degree of the coupling agent, the feeding rate of the glass fiber, the advancing rate of the vibrating conveyer belt and the spraying rate of the atomizing and spraying device to be matched with each other;
3) Putting the uniformly sprayed and infiltrated glass fiber into a large-scale oven for heat treatment at 100 ℃ for 2 hours to complete the process to obtain coupling agent pretreated glass fiber;
and C: continuously adding the long carbon chain copolymerized nylon resin, the lubricant and the antioxidant into a high-speed batching stirrer, and mixing for 10min at a high speed to obtain a pre-mixed mixture;
step D: melting and extruding the premixed mixture and the coupling agent pretreated glass fiber through a TE-75 parallel double-screw extruder, wherein the premixed mixture is added by a main feeder, the coupling agent pretreated glass fiber is added by a side feeder, the temperatures of a first zone, a second zone, a third zone, a fourth zone, a fifth zone, a sixth zone, a seventh zone, an eighth zone, a ninth zone and a machine head of the extruder are sequentially set to be 260 ℃, 280 ℃, 270 ℃, 260 ℃, 250 ℃, 220 ℃, 210 ℃ and 270 ℃, the temperature control error control range is +/-30 ℃, the rotating speed is set to be 250r/min, and the rotating speed error control range is +/-50 r/min; and after extrusion, carrying out water cooling, blow-drying, granulating, homogenizing and drying to obtain the long carbon chain copolymerized nylon composite material in the application embodiment.
The amounts of the respective raw materials in the composite materials of application example 1 and comparative examples 1 to 2 are shown in table 1:
table 1: application example 1 and comparative examples 1 to 2
| Composite Components and weight content (%) | Example 1 | Comparative example 1 | Comparative example 2 |
| The long carbon chain copolymerized nylon prepared by the invention | 37 | / | / |
| Commercially available PA6 | / | 37 | 39 |
| Glass fiber | 60 | 60 | 60 |
| The coupling agent prepared by the invention | 2 | / | / |
| Commercially available coupling agents | / | 2 | / |
| Antioxidant and lubricant | 1 | 1 | 1 |
Note: wherein PA6 is Yueyang Ba Ling petrochemical chemical fiber company YH400, and Ubbelohde viscosity is 2.4; the glass fiber is Taishan glass fiber Co.Ltd T4355; the commercially available coupling agent is KH550 of Chinese academy of sciences; the antioxidant and the lubricant are both a mixture of antioxidant 168, antioxidant 1098 and TAF in a mass ratio of 1: 2.
The properties of the resulting composites were tested according to the relevant standards and the results are shown in table 2:
TABLE 2 physical Properties of composite materials obtained by Using examples and comparative examples
The data in table 2 show that the long carbon chain nylon copolymerized composite material prepared by the present invention uses the long carbon chain nylon resin prepared by the present invention and the dendritic silane-polyamide-amine polymer prepared by the present invention for coupling, the long carbon chain copolymerized nylon obtains a polymer base material capable of better coating the inorganic filler, the contact area between the inorganic material and the organic resin matrix is increased by preferably selecting the special-shaped glass fiber, the rigidity of the composite material of the present invention is further improved, meanwhile, the glass fiber is pretreated by the dendritic coupling agent, the structural particularity of the coupling agent enables the nylon base material of the present invention to be more fully linked with the glass fiber interface, the compatibility is improved, the bonding force between the resin matrix and the glass fiber is further enhanced, and the mechanical properties of the composite material can be obviously changed due to the special structure of the coupling agent.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (7)
1. A high-rigidity long-chain copolymerized nylon composite material is prepared from the following raw materials in percentage by weight:
long carbon chain copolymerized nylon base material: 30-50%;
glass fiber: 50 to 70 percent;
coupling agent: 1 to 4 percent;
other auxiliary agents: 1 to 4 percent;
the synthesis method of the long carbon chain copolymerized nylon comprises the following steps:
(1) The following monomers were prepared:
monomer A: an amino acid or a lactam;
a monomer B: an aliphatic diamine;
a monomer C: an aliphatic dibasic acid;
(2) And (3) performing salt forming reaction, and condensing the monomer B and the monomer C according to a molar ratio of 1:
(3) Polymerization reaction: polycondensing the product D and the monomer A to obtain long carbon chain copolymerized nylon;
the coupling agent is dendritic silane-polyamide-amine polymer, and the structure of the coupling agent is as follows:
wherein, the end functional group R of the finished product is two of R1 and R2, and R1: the quantitative ratio of R2 is 1:2-2:1; the preparation method of the high-rigidity long-chain copolymerized nylon composite material specifically comprises the following steps:
step A: diluting the dendritic silane-polyamide-amine polymer with distilled water to obtain a coupling agent hydrolysate;
and B, step B: b, treating the glass fiber by using the coupling agent hydrolysate obtained in the step A;
and C: adding the long carbon chain copolymerized nylon resin, the lubricant and the antioxidant into a high-speed batching mixer, and mixing to obtain a pre-mixed mixture;
step D: and D, melting and extruding the premixed mixture obtained in the step C and the glass fiber pretreated by the coupling agent through a TE-75 parallel double-screw extruder, and performing water cooling, blow drying, grain cutting, homogenization and drying after extrusion to obtain the long carbon chain copolymerized nylon composite material.
2. The high-rigidity long-chain copolymerized nylon composite material as claimed in claim 1, wherein the contents of the raw materials are as follows:
long carbon chain copolymerized nylon substrate: 35 to 45 percent;
glass fiber: 55-65 percent;
coupling agent: 1 to 2 percent;
other auxiliary agents: 1 to 3 percent.
3. The high rigidity long chain copolymerized nylon composite material of any one of claims 1-2, wherein the glass fiber is selected from one or more of taishan glass fiber ltd T4355, chongqing international composite material ltd ECS301HP-3-M4, and chongqing international composite material ltd ECS301 HP-3-H/TM; the other auxiliary agents comprise an antioxidant and a lubricant.
4. The high rigidity long chain copolymerized nylon composite material of any one of claims 1-2, wherein the antioxidant is selected from 1098, 168 or a mixture thereof; the lubricant is selected from calcium stearate, TAF or mixtures thereof.
5. The high rigidity long chain copolymerized nylon composite material of claim 1, wherein the step (2) in the synthesis method of the long carbon chain copolymerized nylon is: dissolving the monomer B and the monomer C with the same molar weight in water under the protection of nitrogen, heating to 70-80 ℃, reacting for 2 hours until the reaction solution becomes a clear solution, then adding acetone into the solution, precipitating and filtering the reaction product, washing the obtained filtrate with acetone, filtering, and drying for 24 hours at 58 ℃ to obtain a product D;
the step (3) is to input the product D and the monomer A as well as deionized water or distilled water into an automatic control polymerization kettle with a stirrer, start stirring and continuously raise the temperature when the temperature in the polymerization kettle is heated to 125 ℃, and start exhausting when the temperature reaches 140 ℃ and the air pressure is raised to 6 bar; and in the exhaust process, the temperature in the polymerization kettle is raised to 240-320 ℃, then the water in the reaction is removed under the drive of nitrogen, after the water removal is finished, the copolymerized nylon melt generated in the polymerization kettle is discharged under pressure, the copolymerized nylon melt is cast and formed through a die head, and finally the copolymerized nylon is obtained through cooling and granulating, wherein the mass content of the monomer A in the copolymerized nylon is 5-65%, and the mass content of the intermediate product D is 35-95%.
6. The composite material as claimed in claim 1, 2 or 5, wherein the amino acid or lactam in the preparation method of the long carbon chain copolymerized nylon is one or two of 10-amino n-decanoic acid, 11-amino undecanoic acid and dodecanoic lactam; the aliphatic diamine is one or a mixture of hexamethylene diamine and decamethylene diamine; the aliphatic dibasic acid is one or a mixture of sebacic acid and dodecanedioic acid.
7. The high-rigidity long-chain copolymerized nylon composite material as claimed in claim 1, wherein in the step D, the premixed mixture is added by a main feeder, the coupling agent pretreated glass fiber is added by a side feeder, the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone, the seventh zone, the eighth zone, the ninth zone and the head temperature are sequentially set to 260 ℃, 280 ℃, 270 ℃, 260 ℃, 250 ℃, 220 ℃, 210 ℃ and 270 ℃, the temperature control error control range is +/-30 ℃, the rotation speed is set to 250r/min, and the rotation speed error control range is +/-50 r/min.
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