CN114230969B - Polyoxymethylene composition, and preparation method and application thereof - Google Patents
Polyoxymethylene composition, and preparation method and application thereof Download PDFInfo
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- CN114230969B CN114230969B CN202111593754.9A CN202111593754A CN114230969B CN 114230969 B CN114230969 B CN 114230969B CN 202111593754 A CN202111593754 A CN 202111593754A CN 114230969 B CN114230969 B CN 114230969B
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- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 90
- -1 Polyoxymethylene Polymers 0.000 title claims abstract description 66
- 229930040373 Paraformaldehyde Natural products 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 40
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001519 homopolymer Polymers 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 7
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- JVCJCQIOQITEIF-UHFFFAOYSA-N 2-undecylpropanedihydrazide Chemical compound CCCCCCCCCCCC(C(=O)NN)C(=O)NN JVCJCQIOQITEIF-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 239000012212 insulator Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 114
- 238000000034 method Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 14
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 238000001746 injection moulding Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000008118 PEG 6000 Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OJCIQAXLZMIWQT-UHFFFAOYSA-N 2,5-ditert-butyl-4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(C(C)(C)C)=C(O)C=C1C(C)(C)C OJCIQAXLZMIWQT-UHFFFAOYSA-N 0.000 description 1
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical group CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- XBXODRAZJJCJAR-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)C(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)OP(O)(O)=O Chemical compound C(CCCCCCCCCCCCCCCCC)C(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)OP(O)(O)=O XBXODRAZJJCJAR-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 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
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- OFXSXYCSPVKZPF-UHFFFAOYSA-N methoxyperoxymethane Chemical compound COOOC OFXSXYCSPVKZPF-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZWLFGLCGZUVIEA-UHFFFAOYSA-N nonanedihydrazide Chemical compound NNC(=O)CCCCCCCC(=O)NN ZWLFGLCGZUVIEA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to the technical field of macromolecules, and particularly discloses a polyoxymethylene composition, a preparation method and application thereof. The polyoxymethylene composition comprises the following components in parts by weight: 100 parts of polyoxymethylene polymer, 0.2-1 part of dihydrazide substance, 0.2-5 parts of polyvinyl alcohol substance, 1-5 parts of ethylene-methyl acrylate copolymer and 0.1-2 parts of antioxidant. The invention is beneficial to improving the stability of the polyformaldehyde composition in the processing process, reducing the formaldehyde release amount in the polyformaldehyde processing process and simultaneously reducing the generation of mold scales by designing a reasonable formula.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a polyoxymethylene composition, a preparation method and application thereof.
Background
Polyoxymethylene (POM) is a highly crystalline linear thermoplastic polymer, has excellent mechanical properties, wear resistance, self-lubricating property, oil resistance, chemical resistance and creep resistance, has low water absorption, can maintain the mechanical properties, chemical properties and electrical properties of the polyoxymethylene in a wide temperature range, is an engineering plastic with excellent comprehensive properties, and is widely applied to industries such as automobiles, electronics, electrics, household appliances and the like.
Polyoxymethylene is prepared by reacting (-CH) 2 the-O-chain units being predominantly, in which small amounts of (-CH) 2 CH 2 O-) or (-CH 2 CH 2 CH 2 CH 2 The O-) chain is a macromolecule with a methoxyl ether or hydroxyethyl ether structure at the end group, so that the thermal degradation of the molecular chain of the polyformaldehyde is easy to occur under the action of heat and oxygen in the melt processing process, the thermal degradation is self-catalytic, and a large amount of formaldehyde or formic acid is released to be used as a catalyst to accelerate the degradation of the molecular chain. Therefore, in the modification process of polyoxymethylene, it is important to improve the thermal stability thereof.
At present, a method for improving the thermal stability of polyoxymethylene is generally carried out by adding nitrogen-containing substances of amides or substances containing hydroxyl groups to react with terminal groups of polyoxymethylene. In addition, in addition to formaldehyde and formic acid, there are also low molecular weight oligomers or polymers produced during the extrusion process, which are prone to deposit on the mold surfaces during the injection molding process to form mold scales.
There is disclosed a method for controlling formaldehyde release and mold deposit by controlling the amounts of polyacrylamide and copolymerized nylon, and achieving a certain creep amount. However, the introduction of substances such as copolymerized nylon or EVOH has limited effect of reducing formaldehyde emission, and the addition amount cannot be too much due to the problem of compatibility with polyoxymethylene, otherwise mold scale is easily generated, that is, the formaldehyde emission and the mold scale are contradictory, and it is difficult to achieve both properties to be low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyoxymethylene composition, a preparation method and application thereof. The invention is beneficial to improving the stability of the polyformaldehyde composition in the processing process, reducing the formaldehyde release amount in the polyformaldehyde processing process and simultaneously reducing the generation of mold scales by designing a reasonable formula.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a polyoxymethylene composition, which comprises the following components in parts by weight:
100 parts of polyoxymethylene polymer, 0.2-1 part of dihydrazide substance, 0.2-5 parts of polyvinyl alcohol substance, 1-5 parts of ethylene-methyl acrylate copolymer and 0.1-2 parts of antioxidant;
the dihydrazide substance is at least one of sebacic acid dihydrazide, succinic acid dihydrazide, azelaic acid dihydrazide, dodecanedicarboxylic acid dihydrazide, terephthalic acid dihydrazide and isophthalic acid dihydrazide.
The dihydrazide substance, the polyvinyl alcohol substance and the ethylene-methyl acrylate copolymer in the polyoxymethylene composition act together, so that degradation of a polyoxymethylene molecular chain can be reduced, and a stabilizing effect of polyoxymethylene in a processing process is achieved, thereby reducing formaldehyde release amount in the polyoxymethylene processing process, reducing mold scale and achieving the effect of less formaldehyde release amount and mold scale.
The dihydrazide substance is added into the polyoxymethylene composition, so that the formaldehyde release amount of polyoxymethylene can be obviously reduced, and the formaldehyde molecular chain is further stabilized.
As a preferred embodiment of the polyoxymethylene composition of the present invention, the polyoxymethylene composition comprises the following components in parts by weight:
100 parts of polyoxymethylene polymer, 0.3 to 0.8 part of dihydrazide substance, 0.5 to 3 parts of polyvinyl alcohol substance, 1.5 to 3 parts of ethylene-methyl acrylate copolymer and 0.2 to 1 part of antioxidant.
When the components with the weight portions are selected for the polyoxymethylene composition, the formaldehyde release amount in the polyoxymethylene processing process is less, and meanwhile, the generation of film scale is better reduced.
As a preferred embodiment of the polyoxymethylene composition of the present invention, the polyoxymethylene polymer is a homopolymer composed of an oxymethylene monomer as represented by the formula (I), or a copolymer composed of an oxymethylene monomer as represented by the formula (I) and a monomer as represented by the formula (II), or a mixture of the above homopolymers and copolymers;
formula (I): - (-CH) 2 O-; formula (II): [ (CX) 1 X 2 ) a O]；
X 1 And X 2 The same or different, each independently selected from the following groups: hydrogen, alkyl or aryl, a is an integer from 2 to 6.
As a preferred embodiment of the polyoxymethylene composition of the present invention, the homopolymer is a homopolymer terminated by a chemical reaction of terminal hydroxyl groups to form ester groups or ether groups; the copolymers are either incompletely terminated but have free hydroxyl ends in the comonomer units or are ether terminated.
More preferably, the end groups of the homopolymer are acetate and methoxy groups and the end groups of the copolymer are hydroxy and methoxy groups.
The melt index of the polyoxymethylene polymer is 0.5g/10min to 300g/10min as measured by ASTM D1238 or ISO 1133, preferably the melt index of the polyoxymethylene polymer is 1.0g/10min to 300g/10min, more preferably the melt index of the polyoxymethylene polymer is 2.0g/10min to 50g/10min.
In a preferred embodiment of the polyoxymethylene composition of the present invention, the dihydrazide is at least one of sebacic acid dihydrazide, dodecanedicarboxylic acid dihydrazide, and isophthalic acid dihydrazide.
Primary amine, amide groups and formaldehyde molecules in the dihydrazide substance have stronger reaction characteristics, and the reactivity is stronger than that of nitrogen atoms in the amide, so that the dihydrazide substance has better capability of reducing formaldehyde release amount in the process of polyoxymethylene processing. The dihydrazide substances of the types can reduce the release amount of formaldehyde in the polyformaldehyde, and simultaneously reduce the generation of scale in the injection molding process.
Excessive dihydrazide may also cause precipitation during injection molding, thereby enhancing the formation of mold scales. Therefore, the invention selects the specific parts by weight of dihydrazide substances, reduces the formation of mold scales and simultaneously reduces the release amount of formaldehyde.
As a preferable embodiment of the polyoxymethylene composition of the present invention, the polyvinyl alcohol is polyethylene glycol, and the molecular weight of the polyethylene glycol is 4000-20000. More preferably, the polyethylene glycol has a molecular weight of 4000 to 15000.
As a preferred embodiment of the polyoxymethylene composition of the present invention, the ethylene-methyl acrylate copolymer is a glycidyl methacrylate grafted ethylene-methyl acrylate copolymer, and the grafting ratio is 3 to 8%. More preferably, the grafting ratio is 5% to 8%.
The invention limits the molecular weight of polyethylene glycol and the grafting rate of glycidyl methacrylate, and realizes the comprehensive balance of the polyoxymethylene composition in terms of formaldehyde release amount and mold scale.
As a preferred embodiment of the polyoxymethylene composition of the present invention, the antioxidant is a hindered phenol type antioxidant.
More preferably, the hindered phenolic antioxidant is 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 2, 5-di-tert-butyl-4-hydroxybenzyl dimethylamine, diethyl-3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, stearyl-3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 3, 5-di-tert-butyl-4-hydroxyphenyl-3, 5-distearyl-thiotriazolylamine, 2, 6-di-tert-butyl-4-hydroxymethylphenol, 2, 4-di- (N-octylthio) -6- (4-hydroxy-3, 5-di-tert-butylglycerylether) -1,3, 5-triazine, N '-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamide), N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) hexamethylenediamine, stearyl-3, 5-di- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoate, pentaerythritol, 3-di- (3-tert-butyl-4-hydroxyphenyl) propionate, 3, 5-di- (N-octylthio) -6- (4-hydroxy-3, 5-di-tert-butylglycerylether) -1,3, 5-triazine, at least one of triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], and 2,2' -thiodiethyl-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
More preferably, the hindered phenol antioxidant is a combination of triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] and N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, such as Irganox@245 and Irganox@1098.
The thermal stability of the polyoxymethylene composition can be improved by adding the hindered phenol antioxidant, and when the hindered phenol antioxidant is selected from the raw materials, the thermal stability of the polyoxymethylene composition is higher.
The invention also provides a preparation method of the polyoxymethylene composition, which comprises the following steps:
1) Adding a polyoxymethylene polymer, dihydrazide substances, polyvinyl alcohol substances, an ethylene-methyl acrylate copolymer and an antioxidant into a premixing machine according to the proportion, and mixing to obtain a premix;
2) Adding the premix into a double-screw extruder, carrying out melt extrusion at 180-200 ℃, cooling and granulating to obtain the polyoxymethylene composition.
In addition, the invention also provides application of the polyoxymethylene composition in gears, sliding elements, screws, nuts, pump parts, valve bodies, insulators, electronic equipment parts, coffee maker parts and cutter handles.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a polyformaldehyde composition and a preparation method and application thereof, and the polyformaldehyde composition can reduce the degradation of polyformaldehyde molecular chains and play a role in stabilizing polyformaldehyde in the processing process by adopting the synergistic effect of specific dihydrazide substances, polyvinyl alcohol substances and ethylene-methyl acrylate copolymer grafted by glycidyl methacrylate, thereby reducing the formaldehyde release amount in the processing process of polyformaldehyde, reducing mold scale and achieving the effect of less formaldehyde release amount and mold scale; the invention also limits the molecular weight of polyethylene glycol and the grafting rate of glycidyl methacrylate, and realizes the comprehensive balance of the polyoxymethylene composition in terms of formaldehyde release amount and mold scale.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the following examples and comparative examples, the experimental methods used were conventional methods unless otherwise specified, and the materials, reagents and the like used, unless otherwise specified, were all commercially available.
The starting materials for both examples and comparative examples were commercially available from the following sources:
polyoxymethylene polymer: polyoxymethylene copolymer (formula (II), capped, manufacturer POM KP20, melt index 9g/10min (X1 and X2 are both hydrogen, a is 2);
the dihydrazide is selected from:
sebacic dihydrazide, chemically pure, manufacturer is the scientific development limited company of Wuhan Yuan City;
isophthalic acid dihydrazide, chemically pure, manufacturer is the scientific development limited company of the great city of Wuhan;
dodecanedicarboxylic acid dihydrazide, chemically pure, manufacturer is the scientific development limited company of the great city of Wuhan;
adipic acid dihydrazide is chemically pure, and manufacturers are the scientific development limited company of Wuhan Yuan City;
polyethylene glycol:
PEG-400 with molecular weight of 400 is manufactured by Junxin chemical industry Co., ltd;
PEG-4000 with molecular weight 4000 is manufactured by Junxin chemical industry Co., ltd;
PEG-6000 with molecular weight of 6000 is manufactured by Junxin chemical industry Co., ltd;
PEG-15000, molecular weight 15000, manufacturer is Shanghai ai research Biotechnology Co., ltd;
PEG-20000 with molecular weight of 20000 is manufactured by Shanghai ai research Biotechnology Co., ltd;
PTW: the grafting rate of the glycidyl methacrylate is 5 percent, and the manufacturer is DuPont company in the United states;
the ethylene-methyl acrylate copolymer D1 grafted by the glycidyl methacrylate has the grafting rate of 3 percent and the brand KT-33, and the manufacturer is Shenyang Ketong plastic Co., ltd;
ethylene-methyl acrylate copolymer D2 grafted with glycidyl methacrylate, the grafting rate of the glycidyl methacrylate is 8%, and the brand is AX8900, AX, france;
ethylene-methyl acrylate copolymer D3 grafted by glycidyl methacrylate, the grafting rate of the glycidyl methacrylate is 1.5 percent, the brand KT-35A is produced by Shenyang Kogyo Plastic Co., ltd;
an antioxidant: formulation of triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] (trade name Irganox 245) and N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (Irganox 1098).
Examples 1 to 24
Examples 1-24 provide polyoxymethylene compositions having the following formulation in parts by weight:
adding the components into a premixing machine according to a proportion, uniformly mixing for 1-2min to obtain a premix, feeding the premix into a double-screw extruder from a main feeding port, and carrying out melt extrusion and granulation to obtain the polyoxymethylene composition. Wherein, the temperature settings of each heating area from the feeding port to the die head are respectively: the temperature of the first region to the fourth region is 180-190 ℃, the temperature of the fifth region to the ninth region is 190-200 ℃, and the rotating speed of the host machine is 300-400 revolutions per minute.
Comparative examples 1 to 9 provide polyoxymethylene compositions having the formulations shown in Table 2 in parts by weight, and the preparation methods were referred to the preparation methods of examples 1 to 24.
TABLE 1
TABLE 2
The polyoxymethylene compositions prepared in examples 1 to 24 and comparative examples 1 to 9 were subjected to performance tests, each of which was as follows:
1) Tensile properties: tensile property test the test was carried out according to ASTM D638-2014, the test specimen size was 168 mm. Times.13 mm. Times.3.2 mm, the test speed was 50mm/min, and the test apparatus was an electronic tensile testing machine of Zwick company, germany.
2) Notched Izod impact Strength: the test was performed according to ISO180-2019, type A notch, sample size 80mm 10mm 4mm, test equipment was Tinius Olisen impact tester from Wil1ow Grove, U.S.A.
3) Formaldehyde release amount: formaldehyde emission tests were carried out according to the VDA 275 test standard, and the specific procedure is as follows:
the polyoxymethylene composition was injection molded at 190-200 c into square plates with 100mm x 2mm dimensions, then cut into 100mm x 40mm x 2mm dimension products, the injection molded samples were secured in 1 liter polyethylene bottles containing 50ml distilled water, the articles were kept free of contact with water, the bottles were sealed and baked in an oven at 60 c for 3 hours. Then 10ml of the aqueous solution was sampled from the polyethylene bottle, 10ml of a standard solution of acetylacetone and 10ml of ammonium acetate was added, and after a period of time, the degree of coloration of the water in the bottle was analyzed by a UV spectrophotometer, and then the formaldehyde content was calculated.
4) Mold scale:
the mold scale evaluation method comprises the following steps:
a. the mold deposit was evaluated using square plates of 100 x 1.5mm thickness;
b. injection molding process using a claus meffy bench (model CX 160-750): continuously injecting 300 moulds at a medium-high speed at a material temperature of 200 ℃, and evaluating the grade of mould scale through visual inspection and weighing; before each injection molding, a small steel sheet is attached to a die scale collecting position, and the weight of the die scale is judged by weighing the weight change of the small steel sheet before and after the die scale collecting position.
c. Visual scale classification:
stage 1: after continuous injection molding, the surface of the mold is smooth and clean, and the weight of the mold scale is less than 0.1mg;
2 stages: trace substances are deposited on the surface of the die after continuous injection molding, wherein the weight of the die scale is 0.1-0.5mg;
3 stages: after continuous injection molding, more substances are deposited on the surface of the mold, and the weight of the mold scale is 0.5-2mg;
4 stages: after continuous injection molding, substances are deposited on the surface of the whole mold, and the weight of the mold is more than 2mg;
the test results are shown in Table 3.
TABLE 3 Table 3
According to the data of Table 3, the polyoxymethylene compositions prepared in examples 1 to 9 were significantly reduced in formaldehyde emission and less in mold deposit generation; examples 10 to 11 used different dihydrazide species, the prepared polyoxymethylene compositions had less formaldehyde emissions, less mold deposit measured and good comprehensive properties.
Examples 12 to 15, which are prepared from different parts by weight of sebacic dihydrazide, can reduce the release amount of formaldehyde in polyoxymethylene and simultaneously reduce the generation of mold scale in the injection molding process, wherein the effects of examples 3 and 13 to 15 are better than those of example 12.
Examples 16-18 used polyethylene glycols of different molecular weights, examples 3, 16, 17 were better than example 18, so that the polyoxymethylene compositions were better in terms of formaldehyde release and mold deposit.
Examples 19 and 20 used glycidyl methacrylate with a grafting ratio of 3% to 8% to achieve a comprehensive balance of the polyoxymethylene composition in terms of formaldehyde release amount and mold deposit.
In comparative example 1, adipic dihydrazide was used as dihydrazide, but the formaldehyde emission of the prepared composition was small, but the mold scale was generally 3-level, indicating that the selection of dihydrazide capable of reducing both the formaldehyde emission and the mold scale was specific.
Comparative example 2 increased the level of sebacic dihydrazide and the amount of formaldehyde released during processing of the polyoxymethylene composition was small, but mold scales were generally 3-level, indicating that the specified level of sebacic dihydrazide was required to simultaneously reduce the amount of formaldehyde released and mold scales.
Comparative example 3 and comparative example 4 used polyethylene glycol having a molecular weight of 400, which produced compositions with a significant increase in mold build-up during injection molding, demonstrated that the low molecular weight polyethylene glycol had a significant impact on the mold build-up performance of the polyoxymethylene compositions.
The comparative example 5 improves the weight part of PEG-6000 to 10 parts, the mold scale of the composition after injection molding is obviously increased, the tensile strength and the notched Izod impact strength are also reduced, and the selection of the content of polyethylene glycol has great influence on the formaldehyde release amount and the mold scale. When the weight portion of polyethylene glycol is 1-5 portions, the combination property of the composition is better.
In comparative example 6, the PTW is more than 1 to 5 parts by weight, the mold scale of the composition after injection molding is obviously increased, the tensile strength is reduced, and the impact strength is improved; comparative example 7 contained no PTW, and the mold deposit after injection molding of the composition was significantly increased; comparative example 8 does not contain dihydrazide-type substances, and the formaldehyde release amount generated in the processing process of the polyoxymethylene composition is excessive; when the grafting ratio of the glycidyl methacrylate in the comparative example 9 is less than 3% -8%, the formaldehyde release amount generated by the polyoxymethylene composition is more.
According to the invention, through the synergistic effect of the specific dihydrazide substance, the polyvinyl alcohol substance and the ethylene-methyl acrylate copolymer grafted by the glycidyl methacrylate, the degradation of a polyformaldehyde molecular chain can be reduced, and the stabilizing effect of the polyformaldehyde in the processing process is achieved, so that the formaldehyde release amount in the processing process of the polyformaldehyde is reduced, and meanwhile, the mold scale is reduced, and the effect of less formaldehyde release amount and less mold scale is achieved.
The invention adopts the grafting rate of polyethylene glycol and glycidyl methacrylate with proper molecular weight, and ensures the comprehensive performance of the polyoxymethylene composition in formaldehyde release amount, mold scale and square plate color.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The polyoxymethylene composition is characterized by comprising the following components in parts by weight:
100 parts of polyoxymethylene polymer, 0.2-1 part of dihydrazide substance, 1-5 parts of polyvinyl alcohol substance, 1-5 parts of ethylene-methyl acrylate copolymer and 0.1-2 parts of antioxidant;
the dihydrazide substance is at least one of sebacic acid dihydrazide, isophthalic acid dihydrazide and dodecanedicarboxylic acid dihydrazide;
the polyvinyl alcohol substance is polyethylene glycol, and the molecular weight of the polyethylene glycol is 4000-20000;
the ethylene-methyl acrylate copolymer is an ethylene-methyl acrylate copolymer grafted by glycidyl methacrylate, and the grafting rate is 3-8%.
2. The polyoxymethylene composition of claim 1, comprising the following components in parts by weight:
100 parts of polyoxymethylene polymer, 0.3 to 0.8 part of dihydrazide substance, 0.5 to 3 parts of polyvinyl alcohol substance, 1.5 to 3 parts of ethylene-methyl acrylate copolymer and 0.2 to 1 part of antioxidant.
3. The polyoxymethylene composition of claim 1, wherein the polyoxymethylene polymer is a homopolymer composed of a oxymethylene monomer represented by the formula (I), or a copolymer composed of a oxymethylene monomer represented by the formula (I) and a monomer represented by the formula (II), or a mixture of the above homopolymers and copolymers;
formula (I): - (-CH) 2 O-; formula (II): [ (CX) 1 X 2 ) a O]；
X 1 And X 2 The same or different, each independently selected from the following groups: hydrogen, alkyl or aryl, a is an integer from 2 to 6.
4. A polyoxymethylene composition according to claim 3 wherein the homopolymer is a homopolymer terminated by a chemical reaction of terminal hydroxyl groups to form ester groups or ether groups; the copolymers are either incompletely terminated but have free hydroxyl ends in the comonomer units or are ether terminated.
5. The polyoxymethylene composition of claim 1 wherein the antioxidant is a hindered phenol type antioxidant.
6. A process for preparing a polyoxymethylene composition as set forth in any one of claims 1 to 5, comprising the steps of:
1) Adding a polyoxymethylene polymer, dihydrazide substances, polyvinyl alcohol substances, an ethylene-methyl acrylate copolymer and an antioxidant into a premixing machine according to the proportion, and mixing to obtain a premix;
2) Adding the premix into a double-screw extruder, carrying out melt extrusion at 180-200 ℃, cooling and granulating to obtain the polyoxymethylene composition.
7. Use of the polyoxymethylene composition of any one of claims 1 to 5 in gears, sliding elements, screws, nuts, pump parts, valve bodies, insulators, electronic device parts, coffee maker parts, knife handles.
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