CN110483943B - Polyacetal composition and preparation method thereof - Google Patents
Polyacetal composition and preparation method thereof Download PDFInfo
- Publication number
- CN110483943B CN110483943B CN201910851099.9A CN201910851099A CN110483943B CN 110483943 B CN110483943 B CN 110483943B CN 201910851099 A CN201910851099 A CN 201910851099A CN 110483943 B CN110483943 B CN 110483943B
- Authority
- CN
- China
- Prior art keywords
- polyacetal
- diisocyanate
- temperature
- auxiliary agent
- polyacetal composition
- 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
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 127
- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 125
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 31
- -1 cyclic acetal Chemical class 0.000 claims abstract description 30
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 18
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 11
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 7
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 239000011964 heteropoly acid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 150000007517 lewis acids Chemical group 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 2
- 238000002425 crystallisation Methods 0.000 abstract description 44
- 230000008025 crystallization Effects 0.000 abstract description 42
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 37
- 230000001276 controlling effect Effects 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 238000001746 injection moulding Methods 0.000 description 15
- 238000007599 discharging Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000002667 nucleating agent Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- PVKVBDZRILNPJY-UHFFFAOYSA-N 1-butoxybutane;trifluoroborane Chemical compound FB(F)F.CCCCOCCCC PVKVBDZRILNPJY-UHFFFAOYSA-N 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000012760 heat stabilizer Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- LUWOGHUBWAZEQL-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane trimethoxysilane Chemical compound C(C1CO1)OCC1CO1.CO[SiH](OC)OC LUWOGHUBWAZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polyacetal composition and a preparation method thereof, wherein the polyacetal composition comprises polyacetal and an auxiliary agent; the mass ratio of the polyacetal to the auxiliary agent is 1000: 1-100: 1; the auxiliary agent is prepared by copolymerizing cyclic ether and/or cyclic acetal and isocyanate compounds. The preparation method of the polyacetal composition comprises the following steps: mixing cyclic ether and/or cyclic acetal, an isocyanate compound and a catalyst to prepare an auxiliary agent; the polyacetal and the auxiliary are melt-kneaded to prepare the polyacetal composition. The polyacetal composition prepared by the invention has improved crystallization performance, can improve the thermal stability of the polyacetal, has good structural compatibility and is beneficial to uniform dispersion.
Description
Technical Field
The invention relates to a polyacetal composition, in particular to a polyacetal composition and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
Polyacetal is one of important engineering plastics, and is widely used in industries such as automobiles, instruments, electronic and electrical appliances due to its outstanding strength and rigidity, and excellent properties such as self-lubrication, fatigue resistance and wear resistance.
Polyacetal generally has problems such as high brittleness, high shrinkage, and thermal decomposition during processing, and these problems can be improved by adding an auxiliary agent such as a nucleating agent and a heat stabilizer. The nucleating agent can improve the crystallization rate and the crystallization temperature of the polyacetal, refine crystal grains, further reduce the shrinkage rate, improve the dimensional stability of products, and simultaneously, the improvement of the crystallization rate is also beneficial to shortening the processing and molding period. The addition of the heat stabilizer can inhibit the thermal decomposition problem during the processing of the polyacetal.
Commonly used nucleating agents include organic low-molecular (melamine formal, glycidyl ether trimethoxy silane, etc.), inorganic (talc, montmorillonite, diatomaceous earth, boron nitride, nano zirconium dioxide, etc.), organic high-molecular (polyamide, polyvinylidene fluoride, polytetrafluoroethylene, etc.) and composite systems (polyester compounded with nano calcium carbonate, etc.). However, the organic low-molecular nucleating agent has low melting point and poor stability in the product processing process; the inorganic nucleating agent has the problems of poor compatibility and poor dispersibility; however, the existing organic polymer and composite system nucleating agents also have the problems of single function and incapability of improving the thermal stability of the polyacetal, so that high-content auxiliary agents such as an antioxidant, an acid absorbent, a processing stabilizer and the like are often added into the system to ensure the thermal stability of the polyacetal in the processing process, and the production cost of the polyacetal is greatly improved. For example, chinese patent CN102516706B reports that the use of three additives, i.e., a complex nucleating agent, an antioxidant and a stabilizer, simultaneously takes into account the crystallization performance and stability of polyacetal, not only makes the modification process of polyacetal relatively complicated, but also makes various additives generally expensive, and increases the cost of modified polyacetal.
Disclosure of Invention
The invention aims to solve the technical problem of regulating and controlling the crystallization behavior of polyacetal by an auxiliary agent and simultaneously improving the thermal stability of polyacetal.
In order to solve the above technical problems, an aspect of the present invention is to provide a polyacetal composition having both rapid crystallization property and high thermal stability, comprising a polyacetal and an auxiliary agent which is a copolymer of a cyclic ether and/or a cyclic acetal and an isocyanate compound; also provided is a method for producing a polyacetal composition, which combines a rapid crystallization property and high thermal stability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a polyacetal composition comprising a polyacetal and an auxiliary; the mass ratio of the polyacetal to the auxiliary agent is 1000: 1-100: 1; preferably, the mass ratio of the polyacetal to the auxiliary is 300: 1-800: 1;
the auxiliary agent is prepared by copolymerizing cyclic ether and/or cyclic acetal and isocyanate compounds.
Further, the auxiliary agent is a copolymer of cyclic ether and/or cyclic acetal and isocyanate compound under the action of a catalyst.
The catalyst is Lewis acid or nonvolatile protonic acid; preferably, the catalyst is one or more of boron trifluoride ethyl ether complex, boron trifluoride butyl ether complex, heteropoly acid, isopoly acid, heteropoly acid salt and isopoly acid salt.
The heteropoly acid is preferably silicotungstic acid, silicomolybdic acid, phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid and phosphotungstovanadic acid;
the isopolyacid is preferably molybdic acid, paramolybdic acid, metatungstic acid, paratungstic acid, metavanadate or metavanadate.
The molar ratio of the cyclic ether and/or cyclic acetal to the isocyanate compound is 1000: 1 to 10.
The molar ratio of the catalyst, the cyclic ether and/or the cyclic acetal is 1-80 ppm (ppm is parts per million, dimensionless).
The catalyst is diluted or dissolved by an inactive organic solvent, and the organic solvent is at least one selected from n-hexane, n-heptane, cyclohexane, formic acid, acetic acid, ethyl acetate and methyl formate.
The cyclic ether is one or more of the following compounds: ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, oxetane, 1, 3-dioxolane, 1,3, 5-trioxane;
the cyclic acetal is one or more of the following compounds: propylene glycol formal, diethylene glycol formal, triethylene glycol formal, 1, 4-butanediol formal, 1, 5-pentanediol formal, 1, 6-butanediol formal.
The isocyanate compound is aliphatic or aromatic polyisocyanate, preferably one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI) or an autopolymer thereof, p-phenylene diisocyanate (PPDI), 1, 5-Naphthalene Diisocyanate (NDI), 3' -dimethylbiphenyl diisocyanate (TODI), dicyclohexylmethane diisocyanate (HMDI) and isophorone diisocyanate (IPDI) or an autopolymer thereof.
The polyacetal is a granular material or a powdery material of a copolyacetal or a homopolyacetal, and preferably the granular material or the powdery material has a melt flow rate of 6 to 27g/10min under a load of 2.16kg at 190 ℃.
A method for preparing a polyacetal composition, comprising the steps of:
mixing cyclic ether and/or cyclic acetal, an isocyanate compound and a catalyst to prepare an auxiliary agent;
the polyacetal and the auxiliary are melt-kneaded to prepare the polyacetal composition.
The equipment used for melting and mixing the polyacetal and the auxiliary agent is a single-screw extruder, a double-screw extruder, an internal mixer or a double-roller machine; the temperature for melting and kneading the polyacetal and the auxiliary agent is 170-200 ℃.
The invention has the beneficial effects that:
1) the assistant and the polyacetal are polar organic macromolecules, have good structural compatibility, can be uniformly dispersed without a coupling agent, and are beneficial to the simplification of a production process and the reduction of the manufacturing cost of a product;
2) the polyacetal composition added with the auxiliary agent has improved crystallization performance, can increase crystallization temperature and crystallization rate, and can reduce molding shrinkage;
3) the polyacetal compositions containing the auxiliary agent also have improved thermal stability.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
In the examples, the sources of the raw materials are as follows:
1,3, 5-trioxane is a product of Aladdin reagent company, analytically pure, with CAS number 110-88-3;
1, 3-dioxolane is a product of Aladdin reagent company, analytically pure, with CAS number 646-06-0;
1, 4-butanediol formal is a product of Michelle chemical company with CAS number 505-65-7;
cyclohexanoxide is a product of Aladdin reagent, CAS number 286-20-4;
the boron trifluoride butyl ether complex is a product of Tokyo chemical industry Co., Ltd, contains about 30% of boron trifluoride, and has a CAS number of 593-04-4;
the boron trifluoride diethyl etherate complex is a product of Tokyo chemical industry Co., Ltd, contains about 30% of boron trifluoride and has a CAS number of 109-63-7;
n-hexane is a product of Aladdin reagent company, and the CAS number is 110-54-3;
methyl formate is a product of Xilonggao chemical industry Co., Ltd, and the CAS number is 107-31-3;
phosphotungstic acid is a product of Aladdin reagent company, and the CAS number is 12501-23-4;
phosphomolybdic acid is a product of Viro chemical company, and has a CAS number of 11104-88-4;
oxetane is a product of Aladdin reagent, CAS number 503-30-0;
propylene glycol formal is a product of Michelle chemical company, and has a CAS number of 505-22-6;
the p-phenylene diisocyanate is a product of Michelle chemical company, and has a CAS number of 104-49-4;
formic acid is a product of chemical industry, Inc. of Xilonggao, CAS number 64-18-6;
cyclohexane is available from Xilonggao chemical Co., Ltd, and has an analytical purity, CAS number of 110-82-7;
diphenylmethane diisocyanate (MDI) is a product of Vanhua chemical company having a CAS number of 101-68-8;
hexamethylene Diisocyanate (HDI) and its trimer are products of Vanhua chemical company, and the CAS number of HDI is 822-06-0;
toluene Diisocyanate (TDI) is a product of Vanhua chemical company with CAS number 26471-62-5;
dicyclohexylmethane diisocyanate (HMDI) is a product of the Wanhua company with CAS number 5124-30-1;
isophorone diisocyanate (IPDI) is a product of the company Wanhua, and has a CAS number of 4098-71-9;
diatomaceous earth is available from Aladdin reagent, CAS number 91053-39-3;
calcium stearate is a product of Aladdin reagent company, and the CAS number is 1592-23-0;
other materials and reagents are not specifically mentioned and are commercially available.
[ example 1 ]
Preparation of an auxiliary A:
diluting boron trifluoride butyl ether complex with cyclohexane to a concentration of 1 wt% for later use (wt% represents mass percent), then heating 1,3, 5-trioxane to 70 ℃, completely melting, removing water with a molecular sieve and filtering; quickly and uniformly mixing the diluted boron trifluoride butyl ether complex with the purified 1,3, 5-trioxane, controlling the reaction temperature to be 80 ℃, and adding diphenylmethane diisocyanate when the system is turbid, wherein the molar ratio of the boron trifluoride butyl ether complex to the 1,3, 5-trioxane is 10ppm, and the molar ratio of the diphenylmethane diisocyanate to the 1,3, 5-trioxane is 10: 1000, parts by weight; and after the system is completely solidified, crushing and drying the reaction product to obtain the auxiliary A.
Preparation of polyacetal composition:
(1) vacuum drying the polyacetal;
(2) mixing the dried polyacetal and the auxiliary A according to a ratio of 500: 1, and melting and mixing in a double-screw extruder; controlling the rotation speed of the screw to be 200rpm, controlling the temperature of the front section of the extruder to be 170 ℃, the temperature of the middle section of the extruder to be 185 ℃, the temperature of the rear section of the extruder to be 170 ℃ and the cooling temperature to be 35 ℃;
(3) discharging the material from the extruder, carrying out water-cooling bracing, granulating, cooling to room temperature, and crystallizing to obtain a polyacetal composition;
(4) after the polyacetal compositions were dried in vacuo, standard specimens were obtained by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The test results are shown in table 1.
[ example 2 ]
Preparation of an auxiliary B:
dissolving phosphotungstic acid with methyl formate to prepare 0.15 wt% of phosphotungstic acid for later use (the wt% represents the mass percentage), then heating 1,3, 5-trioxane to 70 ℃, removing water by using a molecular sieve after completely melting, and filtering; sequentially adding phosphotungstic acid solution, purified 1,3, 5-trioxane and 1, 3-dioxolane into a reactor, quickly and uniformly mixing, controlling the reaction temperature to be 80 ℃, and adding melted hexamethylene diisocyanate when a system is turbid, wherein the molar ratio of the monomer 1,3, 5-trioxane to the comonomer 1, 3-dioxolane is 25: 1, the molar ratio of phosphotungstic acid to two monomers is 2ppm, and the molar ratio of hexamethylene diisocyanate to the two monomers is controlled to be 5: 1000, parts by weight; and after the system is completely solidified, crushing and drying the reaction product to obtain the auxiliary agent B.
Preparation of polyacetal composition:
(1) vacuum drying the polyacetal;
(2) mixing the dried polyacetal and the assistant B according to the ratio of 100: 1, and melting and mixing in a double-screw extruder; controlling the rotation speed of the screw to be 200rpm, the temperature of the front section of the extruder to be 185 ℃, the temperature of the middle section of the extruder to be 200 ℃, the temperature of the rear section of the extruder to be 185 ℃ and the cooling temperature to be 35 ℃;
(3) discharging the material from the extruder, carrying out water-cooling bracing, granulating, cooling to room temperature, and crystallizing to obtain a polyacetal composition;
(4) after the polyacetal compositions were dried in vacuo, standard specimens were obtained by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The test results are shown in table 1.
[ example 3 ]
Preparation of an auxiliary C:
diluting boron trifluoride diethyl etherate complex with n-hexane to a concentration of 1 wt% (wt% represents mass percent) for later use, then heating 1,3, 5-trioxane to 70 ℃, completely melting, removing water by using a molecular sieve and filtering; sequentially adding diluted boron trifluoride diethyl etherate, purified 1,3, 5-trioxane and 1, 4-butanediol formal into a reactor, quickly and uniformly mixing, controlling the reaction temperature to be 80 ℃, and adding dicyclohexylmethane diisocyanate when a system is turbid, wherein the molar ratio of the monomer 1,3, 5-trioxane to the comonomer 1, 4-butanediol formal is 25: 1, the molar ratio of boron trifluoride diethyl etherate to the two monomers is 20ppm, and the molar ratio of dicyclohexylmethane diisocyanate to the two monomers is 1: 1000, parts by weight; and after the system is completely solidified, crushing and drying the reaction product to obtain the auxiliary agent C.
Preparation of polyacetal composition:
(1) vacuum drying the polyacetal;
(2) the dried polyacetal and the auxiliary C were mixed in the following ratio of 200:1, and melting and mixing in a double-screw extruder; controlling the rotation speed of the screw to be 200rpm, controlling the front section temperature of the extruder to be 175 ℃, the middle section temperature to be 190 ℃, the rear section temperature to be 175 ℃ and the cooling temperature to be 35 ℃;
(3) discharging the material from the extruder, carrying out water-cooling bracing, granulating, cooling to room temperature, and crystallizing to obtain a polyacetal composition;
(4) after the polyacetal compositions were dried in vacuo, standard specimens were obtained by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The test results are shown in table 1.
[ example 4 ]
Preparation of an auxiliary agent D:
dissolving phosphomolybdic acid with formic acid to prepare a 0.15 wt% solution for later use (wt% represents mass percent); the phosphomolybdic acid solution and the epoxy cyclohexane are quickly and uniformly mixed, the reaction temperature is controlled to be 80 ℃, when a system is turbid, isophorone diisocyanate and toluene diisocyanate with equal molar ratio are added, wherein the molar ratio of phosphomolybdic acid to epoxy cyclohexane is 4ppm, and the molar ratio of two used isocyanate substances to epoxy cyclohexane is 1: 1000, parts by weight; and after the system is completely solidified, crushing and drying the reaction product to obtain the auxiliary agent D.
Preparation of polyacetal composition:
(1) vacuum drying the polyacetal;
(2) mixing the dried polyacetal and the auxiliary D according to the ratio of 1000: 1, and melting and mixing in a double-screw extruder; controlling the rotation speed of the screw to be 200rpm, controlling the temperature of the front section of the extruder to be 170 ℃, the temperature of the middle section of the extruder to be 185 ℃, the temperature of the rear section of the extruder to be 170 ℃ and the cooling temperature to be 35 ℃;
(3) discharging the material from the extruder, carrying out water-cooling bracing, granulating, cooling to room temperature, and crystallizing to obtain a polyacetal composition;
(4) after the polyacetal compositions were dried in vacuo, standard specimens were obtained by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The test results are shown in table 1.
[ example 5 ]
Preparation of an auxiliary agent E:
diluting boron trifluoride butyl ether complex with cyclohexane to a concentration of 1 wt% for later use (wt% represents mass percent), then heating 1,3, 5-trioxane to 70 ℃, completely melting, removing water with a molecular sieve and filtering; quickly and uniformly mixing the diluted boron trifluoride butyl ether complex with the purified 1,3, 5-trioxane, controlling the reaction temperature to be 80 ℃, and adding isophorone diisocyanate when the system is turbid, wherein the molar ratio of the boron trifluoride butyl ether complex to the 1,3, 5-trioxane is 80ppm, and the molar ratio of the isophorone diisocyanate to the 1,3, 5-trioxane is 8: 1000, parts by weight; and after the system is completely solidified, crushing and drying the reaction product to obtain the auxiliary agent E.
Preparation of polyacetal composition:
(1) vacuum drying the polyacetal;
(2) mixing the dried polyacetal and the auxiliary E according to the ratio of 300: 1, and melting and mixing in a double-screw extruder; controlling the rotation speed of the screw to be 200rpm, controlling the front section temperature of the extruder to be 175 ℃, the middle section temperature to be 190 ℃, the rear section temperature to be 175 ℃ and the cooling temperature to be 35 ℃;
(3) discharging the material from the extruder, carrying out water-cooling bracing, granulating, cooling to room temperature, and crystallizing to obtain a polyacetal composition;
(4) after the polyacetal compositions were dried in vacuo, standard specimens were obtained by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The test results are shown in table 1.
[ example 6 ]
Preparation of an auxiliary agent F:
diluting boron trifluoride diethyl etherate complex with normal hexane to a concentration of 1 wt% (wt% represents mass percent), sequentially adding the diluted boron trifluoride diethyl etherate complex and oxetane into a reactor, quickly and uniformly mixing, controlling the reaction temperature to be 80 ℃, and adding hexamethylene diisocyanate trimer when the system is turbid, wherein the molar ratio of the boron trifluoride diethyl etherate complex to the oxetane is 50ppm, and the molar ratio of the hexamethylene diisocyanate trimer to the oxetane is 6: 1000, parts by weight; and after the system is completely solidified, crushing and drying the reaction product to obtain the auxiliary agent F.
Preparation of polyacetal composition:
(1) vacuum drying the polyacetal;
(2) the dried polyacetal and the auxiliary F were mixed in a ratio of 800: 1, and melting and mixing in a double-screw extruder; controlling the rotation speed of the screw to be 200rpm, controlling the temperature of the front section of the extruder to be 170 ℃, the temperature of the middle section of the extruder to be 185 ℃, the temperature of the rear section of the extruder to be 170 ℃ and the cooling temperature to be 35 ℃;
(3) discharging the material from the extruder, carrying out water-cooling bracing, granulating, cooling to room temperature, and crystallizing to obtain a polyacetal composition;
(4) after the polyacetal compositions were dried in vacuo, standard specimens were obtained by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The test results are shown in table 1.
[ example 7 ]
Preparation of an auxiliary G:
dissolving phosphotungstic acid with methyl formate to prepare 0.15 wt% solution for later use (wt% represents mass percentage); rapidly and uniformly mixing a phosphotungstic acid solution and epoxy cyclohexane, controlling the reaction temperature to be 80 ℃, and adding toluene diisocyanate when a system is turbid, wherein the molar ratio of phosphotungstic acid to epoxy cyclohexane is 3ppm, and the molar ratio of the toluene diisocyanate to the epoxy cyclohexane is 3: 1000, parts by weight; and after the system is completely solidified, crushing and drying the reaction product to obtain the auxiliary agent G.
Preparation of polyacetal composition:
(1) vacuum drying the polyacetal;
(2) mixing the dried polyacetal and the assistant G according to a ratio of 900: 1, and melting and mixing in a double-screw extruder; controlling the rotation speed of the screw to be 200rpm, controlling the temperature of the front section of the extruder to be 180 ℃, the temperature of the middle section of the extruder to be 195 ℃, the temperature of the rear section of the extruder to be 180 ℃ and the cooling temperature to be 35 ℃;
(3) discharging the material from the extruder, carrying out water-cooling bracing, granulating, cooling to room temperature, and crystallizing to obtain a polyacetal composition;
(4) after the polyacetal compositions were dried in vacuo, standard specimens were obtained by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The test results are shown in table 1.
[ example 8 ]
Preparation of an auxiliary agent H:
dissolving phosphomolybdic acid with formic acid to prepare a 0.15 wt% solution for later use (wt% represents mass percent); rapidly and uniformly mixing phosphomolybdic acid solution and propylene glycol formal, controlling the reaction temperature to be 100 ℃, and adding melted p-phenylene diisocyanate when the system is turbid, wherein the molar ratio of phosphomolybdic acid to propylene glycol formal is 1ppm, and the molar ratio of the p-phenylene diisocyanate to the propylene glycol formal is 2: 1000, parts by weight; and after the system is completely solidified, crushing and drying the reaction product to obtain the auxiliary agent H.
Preparation of polyacetal composition:
(1) vacuum drying the polyacetal;
(2) mixing the dried polyacetal and the auxiliary agent H according to the ratio of 600: 1, and melting and mixing in a double-screw extruder; controlling the rotation speed of the screw to be 200rpm, controlling the temperature of the front section of the extruder to be 170 ℃, the temperature of the middle section of the extruder to be 185 ℃, the temperature of the rear section of the extruder to be 170 ℃ and the cooling temperature to be 35 ℃;
(3) discharging the material from the extruder, carrying out water-cooling bracing, granulating, cooling to room temperature, and crystallizing to obtain a polyacetal composition;
(4) after the polyacetal compositions were dried in vacuo, standard specimens were obtained by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The test results are shown in table 1.
[ example 9 ]
Preparation of pure polyacetals:
(1) vacuum drying the polyacetal;
(2) putting the dried polyacetal into a double-screw extruder, wherein the rotating speed of the screw is 200rpm, the temperature of the front section of the extruder is 170 ℃, the temperature of the middle section of the extruder is 185 ℃, the temperature of the rear section of the extruder is 170 ℃, and the cooling temperature is 35 ℃;
(3) discharging the material from the extruder, water-cooling, bracing, granulating, cooling to room temperature, and crystallizing to obtain pure polyacetal;
(4) after the pure polyacetal was dried in vacuo, standard specimens were drawn off by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured with a vernier caliper. The results are shown in Table 1.
[ example 10 ]
Preparation of polyacetal compositions with nucleating agent addition:
(1) vacuum drying the polyacetal;
(2) uniformly mixing the dried polyacetal and the nucleating agent diatomite according to the mass ratio of 200:1, and then putting the mixture into a double-screw extruder for melting and mixing, wherein the rotating speed of the screws is controlled to be 200rpm, the temperature of the front section of the extruder is 185 ℃, the temperature of the middle section of the extruder is 200 ℃, the temperature of the rear section of the extruder is 185 ℃, and the cooling temperature is 35 ℃;
(3) discharging the mixed materials from an extruder, carrying out water-cooling bracing and granulating, and cooling to room temperature for crystallization to obtain a polyacetal composition;
(4) after the polyacetal compositions were dried in vacuo, standard specimens were obtained by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The results are shown in Table 1.
[ example 11 ]
Preparation of polyacetal composition with Heat stabilizer:
(1) vacuum drying the polyacetal;
(2) uniformly mixing the dried polyacetal and the heat stabilizer calcium stearate according to the mass ratio of 200:1, and then putting the mixture into a double-screw extruder for melting and mixing, wherein the rotating speed of the screws is controlled to be 200rpm, the temperature of the front section of the extruder is 180 ℃, the temperature of the middle section is 195 ℃, the temperature of the rear section is 180 ℃, and the cooling temperature is 35 ℃;
(3) discharging the mixed materials from an extruder, carrying out water-cooling bracing and granulating, and cooling to room temperature for crystallization to obtain a polyacetal composition;
(4) after the polyacetal compositions were dried in vacuo, standard specimens were obtained by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The results are shown in Table 1.
[ example 12 ]
Preparation of a polyacetal composition to which a nucleating agent and a heat stabilizer were added:
(1) vacuum drying the polyacetal;
(2) uniformly mixing the dried polyacetal, a nucleating agent diatomite and a heat stabilizer calcium stearate according to a mass ratio of 200:1:1, and then putting the mixture into a double-screw extruder for melting and mixing, wherein the rotating speed of the screws is controlled to be 200rpm, the temperature of the front section of the extruder is 175 ℃, the temperature of the middle section of the extruder is 190 ℃, the temperature of the rear section of the extruder is 175 ℃, and the cooling temperature is 35 ℃;
(3) discharging the mixed materials from an extruder, carrying out water-cooling bracing and granulating, and cooling to room temperature for crystallization to obtain a polyacetal composition;
(4) after the polyacetal compositions obtained were dried in vacuo, standard specimens were punched out by means of an injection molding machine, the crystallization behavior was characterized by DSC, the thermal stability by TGA and the shrinkage was measured by means of a vernier caliper. The results are shown in Table 1.
The crystallization behavior of the polyacetal compositions or pure polyacetals in the above examples was characterized by differential scanning calorimetry (DSC, available from METTLER TOLEDO, Switzerland), with a sample mass of 8 to 10mg, heating to 200 ℃ at a heating rate of 20 ℃/min under nitrogen atmosphere, holding the temperature for 5min, then cooling to 50 ℃ at a heating rate of 20 ℃/min, recording the crystallization process curve, and recording the initial crystallization temperature, the final crystallization temperature, and the peak crystallization temperature (T.sub.pc) And semi-crystallization time (t)1/2). The inverse of the crystallization half time may reflect the crystallization rate at the experimental temperature.
Thermogravimetric analysis A thermogravimetric analyzer (TGA, from METTLER TOLEDO, Switzerland) was used, with a sample mass of 8-10mg, under nitrogen atmosphere, and a temperature rise rate of 10 ℃/min. The Thermogravimetric (TG) curve records the change process of the sample weight loss along with the temperature under constant temperature rise, and the first derivative of the TG curve to the temperature is obtainedTo a microtransmeric thermogravimetry (DTG) curve. The decomposition temperature corresponding to the maximum weight loss rate on the DTG curve is Tmax。TmaxCan reflect the thermal stability of the test material.
The preparation of the standard sample strips was carried out using a Victor 80 injection moulding machine from EnGEL of Austria, under the injection moulding conditions: the temperature of the charging barrel is 180 ℃ and 190 ℃, the injection pressure is 50MPa, the injection speed is 70mm/s, the pressure maintaining pressure is 40MPa, the pressure maintaining time is 25s, and the temperature of the die is 80 ℃.
And measuring the size of the injection molding sample strip by using a vernier caliper so as to calculate the molding shrinkage in the flow direction and the molding shrinkage in the vertical direction.
The results of the various tests are shown in table 1:
table 1 comparison of results of example characterization
Semi-crystallization time (t) in Table 11/2) The reciprocal of (a) reflects the crystallization rate at the experimental temperature, t1/2The smaller the crystallization rate, the faster the crystallization rate; furthermore, the higher the peak crystallization temperature, the faster the crystallization rate is also indicated; smaller mold shrinkage (flow and vertical) indicates higher dimensional stability of the sample; the higher the thermal decomposition temperature, the higher the thermal stability of the sample.
Analyzing the data in table 1, it can be found that: the polyacetal compositions (examples 1 to 8) to which the above-mentioned additives were added had shorter semicrystallization times, higher peak crystallization temperatures and higher crystallization rates than those of comparative experimental examples 9 to 12. By comparing the molding shrinkage data of examples 1 to 8 and examples 9 to 12, it can be seen that the incorporation of the above-mentioned auxiliary contributes to the improvement of the dimensional stability of the polyacetal composition. As is apparent from the comparison of the thermal decomposition temperatures of examples 1 to 8 and examples 9 to 12, the introduction of the above-mentioned auxiliary agent improves the thermal stability of the polyacetal. When the mass ratio of the polyacetal to the auxiliary agent is 1000: 1-100: 1, the crystallization rate of the polyacetal composition is gradually increased and the dimensional stability and thermal stability are also gradually improved as the proportion of the auxiliary agent is increased. Furthermore, comparing example 3 with example 12, it can be seen that: the addition of the auxiliary agent in the invention can obviously improve the crystallization rate, the dimensional stability and the thermal stability of the polyacetal composition at the same feeding ratio of the polyacetal and the auxiliary agent.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (9)
1. A polyacetal composition comprising a polyacetal and an auxiliary; the mass ratio of the polyacetal to the auxiliary agent is 1000: 1-100: 1;
the auxiliary agent is formed by copolymerizing cyclic ether and/or cyclic acetal and an isocyanate compound;
the auxiliary agent is a copolymer of cyclic ether and/or cyclic acetal and isocyanate compounds under the action of a catalyst; the catalyst is Lewis acid or nonvolatile protonic acid;
the molar ratio of the cyclic ether and/or cyclic acetal to the isocyanate compound is 1000: 1-10;
the molar ratio of the catalyst to the cyclic ether and/or cyclic acetal is 1-80 ppm;
the cyclic ether is one or more of the following compounds: ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, oxetane, 1, 3-dioxolane, 1,3, 5-trioxane;
the cyclic acetal is one or more of the following compounds: propylene glycol formal, diethylene glycol formal, triethylene glycol formal, 1, 4-butanediol formal, 1, 5-pentanediol formal, 1, 6-butanediol formal;
the isocyanate compound is aliphatic or aromatic polyisocyanate.
2. The polyacetal composition according to claim 1, wherein the mass ratio of the polyacetal and the auxiliary is 300: 1-800: 1.
3. the polyacetal composition as set forth in claim 2, wherein said catalyst is one or more selected from the group consisting of boron trifluoride etherate, heteropoly acid, isopoly acid, heteropoly acid salt and isopoly acid salt.
4. The polyacetal composition as claimed in claim 3, wherein the catalyst is diluted or dissolved with an inert organic solvent selected from at least one of n-hexane, n-heptane, cyclohexane, formic acid, acetic acid, ethyl acetate and methyl formate.
5. The polyacetal composition according to claim 4, wherein the isocyanate compound is one or more selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate or an autopolymer thereof, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, 3' -dimethylbiphenyl diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate or an autopolymer thereof.
6. Polyacetal composition according to claim 5, wherein the polyacetal is in the form of pellets or powder of a copolyacetal or a homopolyacetal.
7. The polyacetal composition as set forth in claim 6, wherein the polyacetal has a melt flow rate of 6 to 27g/10min in the form of pellets or powder under a load of 2.16kg at 190 ℃.
8. A method for preparing a polyacetal composition as set forth in any of claims 1 to 7, comprising the steps of:
mixing cyclic ether and/or cyclic acetal, an isocyanate compound and a catalyst to prepare an auxiliary agent;
the polyacetal and the auxiliary are melt-kneaded to prepare the polyacetal composition.
9. The method for producing a polyacetal composition according to claim 8, wherein the temperature for melt-kneading the polyacetal and the auxiliary is 170 to 200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910851099.9A CN110483943B (en) | 2019-09-10 | 2019-09-10 | Polyacetal composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910851099.9A CN110483943B (en) | 2019-09-10 | 2019-09-10 | Polyacetal composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110483943A CN110483943A (en) | 2019-11-22 |
| CN110483943B true CN110483943B (en) | 2022-04-22 |
Family
ID=68557069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910851099.9A Active CN110483943B (en) | 2019-09-10 | 2019-09-10 | Polyacetal composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110483943B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280238B (en) * | 2020-11-05 | 2022-07-19 | 青岛聚合利安工程技术有限公司 | Preparation method of enhanced high-thermal-stability polyacetal composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072710B (en) * | 2013-03-28 | 2016-08-03 | 旭化成株式会社 | The manufacture method of Copolyacetal |
| CN104558460B (en) * | 2013-10-22 | 2017-06-23 | 旭化成株式会社 | The manufacture method of Copolyacetal |
| CN109694543B (en) * | 2018-12-06 | 2022-01-07 | 万华化学集团股份有限公司 | Polyacetal composition and preparation method thereof |
-
2019
- 2019-09-10 CN CN201910851099.9A patent/CN110483943B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110483943A (en) | 2019-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1448708B1 (en) | Polyoxymethylene composite resin composition and articles prepared therefrom | |
| EP2123709A1 (en) | Polyacetal resin composition | |
| JP5354050B2 (en) | Polyacetal resin composition | |
| CN101568595A (en) | Polyacetal resin composition and molded article thereof | |
| WO2010073529A1 (en) | Polyacetal resin composition | |
| EP1630198B1 (en) | Polyacetal resin composition | |
| JP6105305B2 (en) | Polyacetal resin composition and method for producing the same | |
| JP2006111874A (en) | Polyacetal resin composition | |
| TW202016208A (en) | Polyoxymethylene resin composition and metal resin composition containing polyoxymethylene resin, nitrogen-containing compound and fatty acid metal salt | |
| EP3072927A1 (en) | Method for producing polyoxymethylene resin composition | |
| CN110483943B (en) | Polyacetal composition and preparation method thereof | |
| US4181685A (en) | Thermoplastic molding compositions on the basis of polyoxymethylenes | |
| US3848021A (en) | Thermoplastic molding composition on the basis of poly(oxymethylenes) | |
| DE102006050101A1 (en) | Agent for degrading unstable termini, stabilized polyacetal with the agent, method of preparation, composition and molded article | |
| CN110885415A (en) | Antistatic and antibacterial polyacetal resin and preparation method thereof | |
| JPH0439498B2 (en) | ||
| EP3255102B1 (en) | Method for producing polyacetal resin composition | |
| JPH0448822B2 (en) | ||
| CN115850621B (en) | Copolymerized formaldehyde resin composition, metal resin composition taking copolymerized formaldehyde resin composition as raw material, and preparation method and application of metal resin composition | |
| JP3045515B2 (en) | Acetal polymer compound | |
| JP5810649B2 (en) | Resin composition and molded body | |
| EP2123710A1 (en) | Polyacetal resin composition | |
| JP2008001745A (en) | Method for producing polyacetal resin composition | |
| EP0409464A2 (en) | Acetal polymer compositions of high impact strength | |
| JP7550027B2 (en) | Polyacetal resin composition and metal resin composition |
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 |