CN109867905B - POM/TPU alloy material with low VOC content and preparation method thereof - Google Patents
POM/TPU alloy material with low VOC content and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 123
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 101
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 101
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 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 abstract description 20
- 235000019253 formic acid Nutrition 0.000 claims abstract description 20
- 239000002250 absorbent Substances 0.000 claims abstract description 19
- 230000002745 absorbent Effects 0.000 claims abstract description 19
- 238000009835 boiling Methods 0.000 claims abstract description 14
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- 239000000806 elastomer Substances 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 47
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 21
- 239000000347 magnesium hydroxide Substances 0.000 claims description 21
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 18
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 14
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 13
- -1 polyoxymethylene Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 8
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 claims description 4
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 claims description 4
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 claims description 4
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 claims description 4
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 claims description 4
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 239000006096 absorbing agent Substances 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- 239000012855 volatile organic compound Substances 0.000 description 27
- 230000003078 antioxidant effect Effects 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 238000001816 cooling Methods 0.000 description 12
- 238000007599 discharging Methods 0.000 description 12
- 238000005469 granulation Methods 0.000 description 12
- 230000003179 granulation Effects 0.000 description 12
- 238000005491 wire drawing Methods 0.000 description 12
- 235000013824 polyphenols Nutrition 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 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 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- RJZNFXWQRHAVBP-UHFFFAOYSA-I aluminum;magnesium;pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Al+3] RJZNFXWQRHAVBP-UHFFFAOYSA-I 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- BLFRRKIOEASQKD-UHFFFAOYSA-N [O].O=C Chemical compound [O].O=C BLFRRKIOEASQKD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low VOC content POM/TPU alloy material and a preparation method thereof. The alloy material comprises the following components: 100 parts of polyformaldehyde, 5-60 parts of thermoplastic polyurethane elastomer, 10-600ppm of low-boiling point phenols and 50-500ppm of formic acid absorbent. The alloy material disclosed by the invention has low VOC content, excellent impact resistance and high whiteness, and can be used for preparing automotive upholsteries, electronic and electric fittings and other fields.
Description
Technical Field
The invention belongs to the field of polymer blending and polymer molding processing, relates to an alloy material, and particularly relates to a POM/TPU alloy material with low VOC content and a preparation method thereof.
Background
By 2016, the quantity of private cars in China reaches 1.46 hundred million, cars are increasingly popularized as a vehicle, and the safety problem of air quality in the cars is also increasingly emphasized by people, wherein harmful gases in the cars mainly come from Volatile Organic Compounds (VOC) emitted in the cars, which are collectively called VOC (volatile organic compounds), more than 300 of which are identified at present, and benzene, toluene, xylene, free formaldehyde, acetone and the like are mainly harmful. If harmful gas exists in the vehicle for a long time, serious harm is inevitably caused to the human health. The VOC detection of automotive interior parts comprises the whole automobile grade, the part grade and the material grade, and at present, the mainstream test method for the material grade in the automobile industry is a series of methods established by the German automobile industry Association and the German industry Association, and comprises four indexes: VDA270, VDA275, VDA277, DIN 75201. Wherein VDA275 is directed primarily to formaldehyde emissions from automotive interior materials.
A Polyformaldehyde (POM) molecular chain is formed by alternately arranging C-O and twisting the C-O into a spiral shape, the molecular chain is regular in structural phase and easy to crystallize, the high crystallinity (60-80%) of POM endows the material with higher strength and rigidity, meanwhile, polyformaldehyde also has the defects of poor toughness and low notch impact strength, the defects greatly limit the application of POM, in order to expand the application field of POM, a method of blending other polymers and POM is needed to improve the toughness of POM, but the POM and most of the polymers are poor in compatibility. And hydrogen bonds can be formed in the blending process of the Thermoplastic Polyurethane (TPU) and the POM, so that the TPU and the POM have better compatibility, the current TPU toughened POM becomes the only POM toughened and modified product for realizing industrialization, the toughening effect is obvious, and the application of the POM is greatly expanded.
Because of its special molecular structure, POM has poor thermal stability, and especially during production and processing, POM is very likely to volatilize small molecular harmful substances. For POM, the main VOC is derived from free formaldehyde, the reduction of the content of the free formaldehyde in the POM has a very remarkable effect on the reduction of the whole VOC content in the POM, the thermal stability of the POM is improved by industrially adding an antioxidant to capture free radicals, but the method only can improve the thermal stability of the POM and is difficult to effectively remove the free polyformaldehyde generated in the POM; in patent CN201110313331.7, the VOC content of the material is reduced by a method of preparing the stripping masterbatch with porous structural substances such as zeolite, activated carbon, molecular sieve, etc. as the matrix, but when the method is applied to POM/TPU alloy, the major properties of POM/TPU alloy, such as tensile strength, impact strength and elongation at break, are seriously deteriorated.
In patent CN201410252301.3, a method of adding a devolatilization agent and a formic acid absorbent is used to reduce VOC of POM, the devolatilization agent is mainly selected from one or more of ammonia water, triethylamine, triethanolamine, methanol, ethanol, n-propanol, n-butanol, n-pentanol, isopropanol, sec-butanol, and tert-butanol, the formic acid absorbent is mainly selected from one or more of alumina, magnesium oxide, aluminum hydroxide, and magnesium hydroxide, and the formic acid absorbent which selects the devolatilization agent of amines and alcohols and the oxides and hydroxides of magnesium and aluminum can effectively remove free formaldehyde generated during the production and use of POM and neutralize formic acid generated during the degradation of POM. However, the devolatilization effect of amine and alcohol devolatilization agents in POM/TPU alloy materials is poor, and the combination of the devolatilization agent and formic acid absorbent has influence on the mechanical property of POM/TPU alloy products and yellowing of products due to large addition amount, which is not beneficial to the use and dyeing of the products. Therefore, the POM/TPU alloy material needs to be developed, so as to reduce the VOC content and maintain excellent mechanical properties and a low YI value, so as to meet the increasingly strict requirements of people on the air quality in the vehicle.
Disclosure of Invention
The inventors of the present invention have conducted intensive studies to solve the above problems in the prior art, and as a result, unexpectedly found that the combination of low molecular weight phenolic substances and magnesium aluminum hydroxide can significantly reduce the VOC content in the POM/TPU alloy, and at the same time, can significantly improve the thermal stability of the POM/TPU alloy material, reduce the degradation of the POM/TPU during the processing, and maintain the excellent mechanical properties of the material, and the addition amounts of both the combinations are relatively low, thereby avoiding the defects of the two when used alone, and enabling the POM/TPU alloy material to have a relatively low YI value and maintain a relatively high whiteness, thereby completing the present invention.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a low VOC content POM/TPU alloy material is characterized by comprising the following components:
polyoxymethylene: 100 parts by mass;
thermoplastic polyurethane elastomer: 5 to 60 parts by mass, preferably 10 to 40 parts by mass;
phenolic substances with boiling points of 175-220 ℃:1 to 600ppm, preferably 10 to 400ppm, based on the total mass of polyoxymethylene;
formic acid absorbent: 50-500ppm based on the total mass of the polyoxymethylene; preferably 100-300 ppm.
The polyoxymethylene described in the present invention is preferably a homo-or copolyoxymethylene having a melt index of from 1.5 to 40 at 190 ℃/2.16kg, more preferably a homo-or copolyoxymethylene having a melt index of from 2 to 15. Polyoxymethylene is classified into homo-polyoxymethylene and co-polyoxymethylene, co-polyoxymethylene is copolymerized with dioxolane by trimerization, and C-C bond is introduced into polyoxymethylene to improve the thermal stability of POM products, which are available in many markets, such as 4520, 5520 of DuPont, M90, M25 of Yuntanghua GmbH, F20-01, F20-02, F20-03, F20-33 of Korean engineering plastics, N2320, N2640, N2520 of BASF, and the like.
The structural formula of the copolyoxymethylenes is, for example:
wherein n is 500-; m is 10 to 150, preferably 15 to 100.
The thermoplastic polyurethane elastomer is preferably one or more of polyester thermoplastic polyurethane, polyether thermoplastic polyurethane, polycarbonate thermoplastic polyurethane and polycaprolactone thermoplastic polyurethane with the melt index of 5-40 at 190 ℃/2.16Kg, preferably polyester and/or polyether thermoplastic polyurethane with the melt index of 6-35 at 190 ℃/2.16Kg, most preferably polyester thermoplastic polyurethane with the melt index of 8-30 at 190 ℃/2.16Kg, the melt indexes of POM and TPU can be matched by optimizing the melt indexes of the thermoplastic polyurethane, so that the processability and compatibility of the POM/TPU alloy can be improved, and the specific grades comprise WHT-1180, WHT-1185, WHT-1190, WHT-1570, WHT-1575 and WHT-1580 of Wanhua chemical Limited company, WHT-1590, WHT-1680, WHT-1690 and WHT-8180; 58427NAT023, 58610NAT023, 58206NAT031 and 58311NAT028 of Luboemon specialty Chemicals, and Elastollan-B85A, Elastollan-B90A, Elastollan-C85A, Elastollan-C90A, Elastollan-C95A, Elastollan-1180 and the like of BASF.
The low-boiling-point phenolic substance is a phenolic substance with a boiling point of 175-220 ℃, is selected from one or more of phenol, o-cresol, p-cresol, m-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 3, 5-xylenol, o-ethylphenol, p-ethylphenol and m-ethylphenol, is preferably selected from one or more of phenol, o-cresol, p-cresol, m-cresol and o-ethylphenol, and is most preferably selected from phenol, in particular to phenol of Shanghai Mitsui, Jilin petrochemical and Yanshan petrochemical, Alerasha, Shanghai Merril and echiei o-cresol and the like. The low-boiling point phenolic substance can react with free formaldehyde in the POM, so that the free formaldehyde in the alloy is removed, the VOC content of the alloy is reduced, free radicals generated in the preparation of the alloy can be effectively captured, and an excellent antioxidant effect is achieved.
The formic acid absorbent is one or more of oxides or hydroxides of sodium, magnesium and aluminum, preferably one or more of magnesium oxide, aluminum oxide, magnesium hydroxide and aluminum hydroxide, most preferably magnesium hydroxide and aluminum hydroxide, the addition amount of the formic acid absorbent is 50-500ppm, preferably 100-300ppm, based on the total mass of Polyformaldehyde (POM), the specific manufacturer of the magnesium hydroxide has Weifang Hilliron, Hefei Zhongke, Shanghai Yangtze river and the like, the specific manufacturer of the aluminum hydroxide has Jinnan Thai star to carry out chemical industry, Tboeberkang, Guangdong Zhongde resin and the like, and the formic acid absorbent can neutralize formic acid generated by formaldehyde oxygen, prevent the formic acid from catalytically degrading the POM and further reduce the VOC content of the product.
The invention is characterized in that other auxiliary agents can be added, the auxiliary agents are selected from one or more of antioxidant, ultraviolet absorbent, lubricant and light stabilizer, and the addition amount of the antioxidant and the ultraviolet absorbent is 0.1-3% respectively based on the total mass of other components except the auxiliary agents in the composition.
In the low VOC content POM/TPU alloy material of the invention, the VOC content of the alloy according to VDA277 standard is below 10ppm, preferably below 9ppm, further below 8ppm by mass.
The preparation method of the low VOC content POM/TPU alloy material comprises the following steps.
(1) Weighing POM, TPU resin, phenolic substances with the boiling point of 175-220 ℃, formic acid absorbent and optional (existing or nonexistent) processing aids according to the proportion, and mixing in a high-speed mixer;
(2) and adding the uniformly mixed substances into a double-screw extruder, and performing melt extrusion and then drawing and granulating. Preferably, the length-diameter ratio of the double-screw extruder is 44-56:1, the barrel temperature of the double-screw extruder is 180-220 ℃, the screw rotating speed is 200-400RPM, and the vacuum degree of the double-screw extruder is less than-0.05 MPa.
The POM/TPU alloy material with low VOC content can be used for automobile interior parts such as instrument panels, electric switches, safety belt buckles, lifting window switches and the like.
The invention has the following beneficial effects:
according to the low-VOC POM/TPU alloy material, the combination of low-boiling-point phenolic substances and aluminum magnesium hydroxide is added, so that the VOC content in the POM/TPU alloy can be reduced, the VOC content of the prepared POM/TPU alloy material is lower than 10ppm, the degradation of the POM/TPU alloy material in the preparation process can be effectively prevented, the material has low VOC content, excellent mechanical property and a lower YI value, and the material can be applied to automobile interior parts such as instrument panels, electric switches, safety belt buckles and lifting window switches with higher requirements on the VOC content and the mechanical property, and plugging elements, switches, buttons, relays and the like of electronic and electric appliances.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
VOC test methods: the test was performed according to the VDA277 standard using a headspace-gas chromatograph (FID detector). The test specimens are produced at defined locations over the entire cross-section of the structural component, cut into small pieces with a weight of 10-25mg, and the test specimens cannot be heated in the process. Sample weighing the sample was weighed out in terms of vial volume, 1.000 g. + -. 0.001g per 10ml volume (i.e. maximum weighing error 0.1%).
And (4) testing the Yellowness Index (YI), namely adding the particles of the POM/TPU alloy into a transparent test sample cup, placing the sample cup in a color difference instrument of Hunt lab VIS to test the YI value of the product, and judging the degree of deviation from white or yellowing of the product according to the YI value.
Polyoxymethylene: korean engineering plastic F20-02, which is a copolyoxymethylene with a melt index of 9; yuntian M90, the product is polyformaldehyde with melt index of 9; 4520 from dupont, product melt index is copolyoxymethylene of 7; BASF N2520, product is a copolyoxymethylene having a melt index of 7.5.
Thermoplastic polyurethane elastomer, 1180 in Wawawa chemical, the product being a polyester TPU with a melt index of 18; Elastollan-B85A from BASF, product melt index 25 polyester TPU; 1585 in Wanhua chemical, product melt refers to a polyester TPU of 18; 8180 in Wanhua chemistry, product melt refers to a 30 polyether TPU.
The low boiling point phenolic substance is refined phenol of Shanghai Mitsui and Jilin petrochemical industries, and the boiling point of the phenol is 182 ℃; the boiling point of o-cresol of Shanghai Michelle is 190 ℃.
Formic acid absorbent: magnesium hydroxide of the family of fertilizer compounding and aluminum hydroxide of the fine chemical industry of Jinan Taixing.
Antioxidant: BASF antioxidant 245 for Ciba Fine Chemicals.
Example 1
(1) Weighing 2kg of F20-02 copolymerized polyformaldehyde, 0.6kg of 1180 polyether TPU, 200ppm of phenol and 200ppm of aluminum hydroxide (the ppm is calculated by taking the mass of polyformaldehyde as a reference, and the following steps are carried out);
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin screw extruder with a length to diameter ratio of 44:1, the extruder temperature settings were as follows (from feed port to head): 80 deg.C, 180 deg.C, 185 deg.C, 190 deg.C, 195 deg.C, 200 deg.C, 205 deg.C, 200 deg.C, 190 deg.C, 185 deg.C. The temperature of a neck ring die is 185 ℃, the vacuum degree is-0.05 MPa, the extrusion rotating speed is 200RPM, the materials are extruded and then subjected to water-cooling wire drawing granulation, and the prepared alloy material comprises 100 parts of POM, 30 parts of TPU, 200ppm of phenol and 200ppm of aluminum hydroxide based on the weight of the alloy material.
Example 2
(1) Weighing 2kg of F20-02 copolymerized polyformaldehyde, 0.3kg of 1180 polyether TPU, 300ppm of phenol and 100ppm of magnesium hydroxide,
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin screw extruder with a 48:1 aspect ratio, the extruder temperature settings were as follows (from feed port to head): 80 deg.C, 180 deg.C, 185 deg.C, 190 deg.C, 195 deg.C, 200 deg.C, 205 deg.C, 200 deg.C, 190 deg.C, 185 deg.C, 180 deg.C. The temperature of a neck ring mold is 180 ℃, the vacuum degree is-0.06 MPa, the extrusion rotating speed is 200RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material has the POM content of 100 parts by mass, the TPU content of 15 parts by mass, the phenol content of 300ppm and the magnesium hydroxide content of 100 ppm.
Example 3
(1) Weighing 2kg of M90 copolymerized polyformaldehyde, 0.8kg of Elastollab-B85A polyester TPU, 100ppm of phenol and 200ppm of magnesium hydroxide,
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder having a length-to-diameter ratio of 48:1, and the temperatures of the extruder stages were set as shown (from the feed port to the head) at 80 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 210 ℃, 200 ℃, 195 ℃. The temperature of a neck ring mold is 195 ℃, the vacuum degree is-0.07 MPa, the extrusion rotating speed is 300RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material has the POM content of 100 parts by mass, the TPU content of 40 parts by mass, the phenol content of 100ppm and the magnesium hydroxide content of 200 ppm.
Example 4
(1) Weighing 2kg of M90 copolymerized polyformaldehyde, 0.2kg of Elastollab-B80A polyester TPU, 400ppm of phenol, 100ppm of magnesium hydroxide and 24511 g of antioxidant,
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder having a length-to-diameter ratio of 52:1, and the temperatures of the extruder stages were set (from the feed port to the head) at 80 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 210 ℃, 200 ℃, 195 ℃ and 190 ℃. The temperature of a neck ring mold is 190 ℃, the vacuum degree is-0.06 MPa, the extrusion rotating speed is 200RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material comprises 100 parts of POM, 10 parts of TPU, 400ppm of phenol, 100ppm of magnesium hydroxide and 0.5% of antioxidant 245 based on the weight of the alloy material.
Example 5
(1) Weighing 2kg of M90 copolymerized polyformaldehyde, 1.2kg of Elastollab-B80A polyester TPU, 150ppm of phenol, 150ppm of aluminum hydroxide and 2459.6 g of antioxidant,
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin screw extruder with a length to diameter ratio of 52:1, the temperature settings for the extruder stages were as follows (from feed port to head): 80 deg.C, 185 deg.C, 190 deg.C, 195 deg.C, 200 deg.C, 205 deg.C, 210 deg.C, 215 deg.C, 200 deg.C, 195 deg.C, 190 deg.C. The temperature of a neck ring mold is 190 ℃, the vacuum degree is-0.06 MPa, the extrusion rotating speed is 400RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material has the POM content of 100 mass parts, the TPU content of 60 mass parts, the phenol content of 150ppm, the aluminum hydroxide content of 150ppm and the antioxidant 245 content of 0.3 percent of (POM + TPU).
Example 6
(1) Weighing 4520 copolymerized polyformaldehyde 2kg, 1585 polyester TPU 0.4kg, phenol 80ppm, aluminum hydroxide 300ppm, antioxidant 24519.2 g,
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder having a length-to-diameter ratio of 52:1, and the temperatures of the extruder stages were set as shown (from the feed port to the head) at 80 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 210 ℃, 200 ℃, 195 ℃ and 190 ℃. The temperature of a neck ring mold is 190 ℃, the vacuum degree is-0.05 MPa, the extrusion rotating speed is 300RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material has the POM content of 100 parts by mass, the TPU content of 20 parts by mass, the phenol content of 80ppm, the aluminum hydroxide content of 300ppm and the antioxidant 245 content of 0.8 percent of (POM + TPU).
Example 7
(1) Weighing 4520 copolymerized polyformaldehyde 2kg, 1585 polyester TPU 0.1kg, phenol 300ppm, magnesium hydroxide 300ppm,
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder having a length-to-diameter ratio of 52:1, and the temperatures of the extruder stages were set (from the feed port to the head) at 80 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 215 ℃, 210 ℃, 200 ℃, 195 ℃ and 190 ℃. The temperature of a neck ring mold is 190 ℃, the vacuum degree is-0.05 MPa, the extrusion rotating speed is 400RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material contains 100 parts of POM, 5 parts of TPU, 300ppm of phenol and 300ppm of aluminum hydroxide based on the weight of the alloy material.
Example 8
(1) Weighing 2kg of N2520 copolymerized polyformaldehyde, 0.2kg of 8180 polyether type TPU, 50ppm of phenol and 300ppm of aluminum hydroxide,
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder having a length-to-diameter ratio of 48:1, and the temperatures of the extruder stages were set as shown (from the feed port to the head) at 80 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 215 ℃, 210 ℃, 200 ℃ and 195 ℃. The temperature of a neck ring mold is 195 ℃, the vacuum degree is-0.05 MPa, the extrusion rotating speed is 400RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material has the POM content of 100 parts by mass, the TPU content of 10 parts by mass, the phenol content of 50ppm and the aluminum hydroxide content of 300 ppm.
Example 9
(1) Weighing 2kg of M90 copolymerized polyformaldehyde, 0.4kg of 1180 polyester TPU, 300ppm of o-cresol, 100ppm of magnesium hydroxide and 2452 g of antioxidant;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder having a length to diameter ratio of 48:1, and the temperatures of the extruder stages were set as follows (from the feed port to the head) at 80 ℃, 185 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 210 ℃, 205 ℃, 195 ℃ and 190 ℃. The temperature of a neck ring mold is 190 ℃, the vacuum degree is-0.07 MPa, the extrusion rotating speed is 200RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material has the POM content of 100 parts by mass, the TPU content of 20 parts by mass, the phenol content of 300ppm, the magnesium hydroxide content of 100ppm and the antioxidant content of 0.5 percent.
Example 10
(1) Weighing 2kg of M90 copolymerized polyformaldehyde, 0.6kg of 1180 polyester TPU, 300ppm of phenol, 150ppm of magnesium hydroxide and 2454 g of antioxidant;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder having a length-to-diameter ratio of 48:1, and the temperatures of the extruder stages were set as shown (from the feed port to the head) at 80 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 200 ℃, 190 ℃, 185 ℃. The temperature of a neck ring mold is 185 ℃, the vacuum degree is-0.06 MPa, the extrusion rotating speed is 200RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material has the POM content of 100 parts by mass, the TPU content of 30 parts by mass, the phenol content of 300ppm, the magnesium hydroxide content of 150ppm and the antioxidant content of 0.5 percent.
Comparative example 1
(1) Weighing 2kg of M90 copolymerized polyformaldehyde, 0.6kg of 1180 polyester TPU, 10g of n-propanol, 10g of magnesium hydroxide and 245131 g of antioxidant,
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder having a length-to-diameter ratio of 48:1, and the temperatures of the extruder stages were set as shown (from the feed port to the head) at 80 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 200 ℃, 190 ℃, 185 ℃. The temperature of a neck ring mold is 185 ℃, the vacuum degree is-0.06 MPa, the extrusion rotating speed is 200RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material contains 100 parts by mass of POM, 30 parts by mass of TPU, 0.5 part by mass of n-propanol, 0.5 part by mass of magnesium hydroxide and 0.5 part by mass of antioxidant.
Comparative example 2
(1) Weighing 2kg of M90 copolymerized polyformaldehyde, 0.6kg of 1180 polyester TPU, 300ppm of phenol and 245131 g of antioxidant;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder having a length-to-diameter ratio of 48:1, and the temperatures of the extruder stages were set as shown (from the feed port to the head) at 80 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 200 ℃, 190 ℃, 185 ℃. The temperature of the neck ring mold is 185 ℃, the vacuum degree is-0.06 MPa, the extrusion rotating speed is 200RPM, the materials are subjected to water-cooling wire drawing granulation after being extruded, and the prepared alloy material has the POM content of 100 parts by mass, the TPU content of 30 parts by mass, the phenol content of 300ppm and the antioxidant of 0.5 percent.
Table 1 results of performance testing
From the above comparative examples and examples, the VOC content of the product is significantly reduced after adding low molecular weight phenolics and magnesium aluminum hydroxide, and the product has excellent mechanical properties while having a lower yellowness index (YI value).
Claims (21)
1. The POM/TPU alloy material is characterized by comprising the following components:
polyoxymethylene: 100 parts by mass;
thermoplastic polyurethane elastomer: 5-60 parts by mass;
phenolic substances with boiling points of 175-220 ℃: based on the total mass of the polyformaldehyde, the mass is 1-600 ppm;
formic acid absorbent: 50-500ppm based on the total mass of the polyoxymethylene;
the formic acid absorbent is one or more selected from sodium hydroxide, magnesium hydroxide and aluminum hydroxide.
2. The POM/TPU alloy material of claim 1,
thermoplastic polyurethane elastomer: 10-40 parts by mass;
phenolic substances with boiling points of 175-220 ℃: 10-400ppm based on the total mass of polyoxymethylene;
formic acid absorbent: based on 100-300ppm of the total mass of polyoxymethylene.
3. The POM/TPU alloy material of claim 1, wherein said polyoxymethylene is a homo-or copolyoxymethylene having a melt index of 1.5 to 40 at 190 ℃/2.16 kg.
4. The POM/TPU alloy material of claim 3, wherein said polyoxymethylene is a homo-or copolyoxymethylene having a melt index of 2 to 25.
5. The POM/TPU alloy material of any of claims 1 to 4 wherein the copolyoxymethylene has the formula:
wherein n = 500-; m = 10-150.
6. The POM/TPU alloy material of claim 5, wherein n = 1000-; m = 15-100.
7. The POM/TPU alloy material of any one of claims 1 to 4, wherein said thermoplastic polyurethane elastomer is one or more of polyester thermoplastic polyurethane, polyether thermoplastic polyurethane, polycarbonate thermoplastic polyurethane having a melt index of 5 to 40 at 190 ℃/2.16 Kg.
8. The POM/TPU alloy material of claim 7, wherein said thermoplastic polyurethane elastomer is a polyester and/or polyether thermoplastic polyurethane with a melt index of 6-35 at 190 ℃/2.16 Kg.
9. The POM/TPU alloy material of claim 8, wherein said thermoplastic polyurethane elastomer is a polyester thermoplastic polyurethane having a melt index of 8-30 at 190 ℃/2.16 Kg.
10. The POM/TPU alloy material of claims 1 to 4 wherein the phenolic material having a boiling point of 175-220 ℃ is selected from the group consisting of phenol, o-cresol, p-cresol, m-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 3, 5-xylenol, o-ethylphenol, p-ethylphenol, and m-ethylphenol.
11. The POM/TPU alloy material of claim 10 wherein the phenolic material having a boiling point of 175-220 ℃ is selected from the group consisting of phenol, o-cresol, p-cresol, m-cresol, o-ethylphenol.
12. The POM/TPU alloy material of claim 11, wherein said phenolic material having a boiling point of 175-220 ℃ is selected from the group consisting of phenol.
13. POM/TPU alloy material according to any of claims 1 to 4, characterized in that the formic acid absorbent is selected from one or more of magnesium oxide, aluminum oxide, magnesium hydroxide, aluminum hydroxide.
14. The POM/TPU alloy material of claim 13, wherein the formic acid absorbent is selected from the group consisting of magnesium hydroxide and aluminum hydroxide.
15. POM/TPU alloy material according to any of claims 1 to 4, characterized in that it further comprises auxiliaries, selected from one or more of antioxidants, UV absorbers, lubricants, light stabilizers, in amounts of from 0.1 to 3% by weight, based on the total mass of the other components of the composition, excluding auxiliaries.
16. POM/TPU alloy material according to any of claims 1 to 4, characterized in that the VOC content of the alloy tested according to the VDA277 standard is below 10 ppm.
17. The POM/TPU alloy material of claim 16, wherein the VOC content of the alloy tested according to VDA277 standard is less than 9 ppm.
18. The POM/TPU alloy material of claim 17, wherein the VOC content of the alloy tested according to VDA277 standard is less than 8 ppm.
19. The process for preparing a POM/TPU alloy material as set forth in any of claims 1-18, wherein:
(1) weighing polyformaldehyde, a thermoplastic polyurethane elastomer, a phenolic substance with a boiling point of 175-220 ℃, a formic acid absorbent and an optional processing aid in proportion, and mixing in a high-speed mixer;
(2) and adding the uniformly mixed substances into a double-screw extruder, and performing melt extrusion and then drawing and granulating.
20. The preparation method as claimed in claim 19, wherein the length-diameter ratio of the twin-screw extruder is 44-56:1, the barrel temperature of the twin-screw extruder is 180-220 ℃, the screw rotation speed is 200-400RPM, and the vacuum degree of the twin-screw extruder is less than-0.05 MPa.
21. Use of the POM/TPU alloy material of any of claims 1-18 or the POM/TPU alloy material obtained by the method of claim 19 or 20 for automotive instrument panels, electrical switches, seat belt buckles, lifter switches, or plug elements, switches, buttons, relays of electronic appliances.
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