CN114685932B - Polyoxymethylene composition, and preparation method and application thereof - Google Patents
Polyoxymethylene composition, and preparation method and application thereof Download PDFInfo
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- CN114685932B CN114685932B CN202111531793.6A CN202111531793A CN114685932B CN 114685932 B CN114685932 B CN 114685932B CN 202111531793 A CN202111531793 A CN 202111531793A CN 114685932 B CN114685932 B CN 114685932B
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- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 51
- 229930040373 Paraformaldehyde Natural products 0.000 title claims abstract description 48
- -1 Polyoxymethylene Polymers 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 125000003277 amino group Chemical group 0.000 claims abstract description 16
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims abstract description 7
- 238000012360 testing method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 3
- 230000007774 longterm Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 150000003141 primary amines Chemical class 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- KSJNLHWGUSIAIF-UHFFFAOYSA-N 2-[2-[2-[3-(4-hydroxy-3,5-dimethylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(4-hydroxy-3,5-dimethylphenyl)propanoate Chemical compound CC1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C)C(O)=C(C)C=2)=C1 KSJNLHWGUSIAIF-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 compound 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 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
- 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
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000012668 chain scission Methods 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
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OFXSXYCSPVKZPF-UHFFFAOYSA-N methoxyperoxymethane Chemical compound COOOC OFXSXYCSPVKZPF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 238000004383 yellowing 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
- C08L59/04—Copolyoxymethylenes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyoxymethylene composition, which comprises the following components in parts by weight: 100 parts of copolymerized formaldehyde resin; 1.5-5 parts of polyethyleneimine; wherein the mole percentage of primary amine in the polyethyleneimine accounting for the sum of amino groups is more than or equal to 37mol percent. According to the invention, a certain amount of polyethyleneimine synergistic copolymerized formaldehyde resin with a specific structure is added, so that the formaldehyde release amount of the formaldehyde composition can be effectively reduced, the creep resistance can be improved, and the requirement of long-term wear-resistant parts can be met.
Description
Technical Field
The invention relates to the technical field of high polymer materials, 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.
In one aspect, POM is in the form of (-CH) 2 -O-) chain is mainly, and the end group is a macromolecule with methoxyl ether or hydroxyethyl ether structure. This results in the fact that POM is susceptible to chain scission under the action of heat and oxygen during melt and shear processing, and that this thermal decomposition is autocatalytic and gives off a large amount of formaldehyde. Thus, in the creation of the invention of polyoxymethylene compositions, formaldehydeInhibition of the amount released is an important aspect. In the prior art, the formaldehyde release in the polyoxymethylene resin is reduced mainly by the following two methods:
1. the melt processing stability is improved to reduce molecular chain breakage caused by the process of melting (more than 180 ℃) and shearing of the polyoxymethylene resin, so that formaldehyde generation is reduced. The addition of acrylamide and boric acid compound to polyoxymethylene resin is described in Japanese laid-open patent publication No. Hei 10-1592. However, the additives in the above-mentioned methods are processes which do not withstand high temperature shear, cause yellowing of the polymer, and are liable to exude in the polymer to cause formation of precipitates in the mold, thus limiting applicability. Chinese application CN1440441a discloses a stable thermoplastic molding material, wherein the addition of 1ppb-1% of polyethylenimine to polyoxymethylene resin can improve the thermal stability of the material, to reduce the mass loss rate after baking at 220 ℃, to improve the color stability after baking at 220 ℃. However, it is known from the technical effects of examples and comparative examples in this patent that the color stability thereof is still insufficient for most of the scene requirements, and the mass reduction rate thereof is only indicative of the VOC emission (including moisture, since the polyethyleneimine added in comparative document 1 is an aqueous solution, a small amount of water remains in the composition in practice, and the mass loss rate thereof includes a part of the amount of water), but is not indicative of the formaldehyde emission amount thereof.
2. The formaldehyde is adsorbed by adding the adsorbent, so that the formaldehyde release is reduced. Such as porous fillers commonly used, and the like. However, the addition amount of the porous fillers needs to reach more than 5% to have obvious formaldehyde adsorption effect, so that other modification directions of the composite material can be influenced, and particularly the porous adsorbents have a large influence on the toughness of the polyoxymethylene composite material, and the application of the polyoxymethylene composite material can be influenced when the addition amount is excessive.
On the other hand, POM resins, during long-term use, may cause breakage of POM molecular chains due to the action of force and heat, thereby causing an increase in creep thereof. POM products generally need to be applied to wear-resistant products, such as gears, sliding elements, screws, nuts, pump components, valve bodies and the like, and the products have long service life, and creep resistance is an important performance index, and if the creep resistance is poor, the product is easy to fail in the long-term use process, so that potential safety hazards are caused. In the prior art, the creep resistance of the material is improved mainly by adding amide substances. Such as chinese patent application CN105829443a, but this material tends to cause the formation of a precipitate in the mould, which is used in relatively low amounts.
Disclosure of Invention
The invention aims to provide a polyoxymethylene composition with low formaldehyde emission and a preparation method thereof.
The invention is realized by the following technical scheme:
the polyoxymethylene composition comprises the following components in parts by weight:
100 parts of copolymerized formaldehyde resin;
1.5-5 parts of polyethyleneimine;
wherein the mole percentage of primary amine in the polyethyleneimine accounting for the sum of amino groups is more than or equal to 37mol percent.
Preferably, 1.9 to 3.5 parts of polyethyleneimine.
More preferably, 2.7 to 3 parts of polyethyleneimine.
The preferred range of polyethyleneimine content provides better creep resistance.
Preferably, the mole percentage of primary amine in the polyethyleneimine is more than or equal to 40mol percent of the total amino groups; more preferably not less than 50mol%; it is further preferred that the molar percentage of primary amine in the polyethyleneimine is more than or equal to 90mol% based on the total amino groups. The primary amino content can be determined by 13 CNMR assay.
The melt index range of the copolyformaldehyde resin capable of achieving the purpose of the invention is 0.5-300g/10min, the test condition is 190 ℃/2.16KG, and the test standard is ISO 1133:2005.
Preferably, the copolyoxymethylene resin is endcapped, typically with acetic anhydride.
Whether 0-1 part of antioxidant is added or not can be determined according to actual conditions.
The antioxidant may be: 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-bis- (n-octylsulfanyl) -6- (4-hydroxy-3, 5-di-tert-butylglycerylethyl ether) -1,3, 5-triazine; n, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide); n, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine; octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; triethylene glycol-bis [3- (3, 5-dimethyl-4-hydroxyphenyl) propionate ]; triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ];2,2' -thiodiethyl-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like.
The preparation method of the polyoxymethylene composition comprises the following steps: according to the proportion, the components are evenly mixed and extruded and granulated by a double-screw extruder to obtain the polyoxymethylene composition, wherein the temperature range of the screw is 180-200 ℃ and the rotating speed is 250-400 rpm.
The polyoxymethylene composition of the present invention is applied to gears, sliding members, screws, nuts, pump parts, valve bodies, etc.
The invention has the following beneficial effects:
according to the invention, a certain amount of polyethyleneimine with primary amine accounting for more than or equal to 37mol% of the total amino groups is added into the copolyformaldehyde resin, so that on one hand, the primary amino groups and formaldehyde have good reactivity, formaldehyde released from the polyformaldehyde composition can be adsorbed, the purpose of reducing formaldehyde release for a long time is achieved, and the formaldehyde adsorption capacity is increased along with the increase of primary amine content; on the other hand, through the addition of the polyethyleneimine and the investigation of the content of the primary amine group, the primary amine group has stronger capability of reacting with formaldehyde than the secondary amine group, so that the polyethyleneimine can stabilize the polyformaldehyde molecular chain more along with the increase of the content of the primary amine in the polyethyleneimine, and the POM molecular chain is kept stable for a long time in the long-term use process, so that the creep resistance of the POM resin is improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The sources of the raw materials used in the examples and comparative examples are as follows:
copolyoxymethylene resin A: brand POM KP20, blocked, melt index 9 g/10min (190 ℃/2.16 KG), talcum, germany;
copolyoxymethylene resin B: brand POM CE67FC, blocked, melt index 27 g/10min (190 ℃/2.16 KG), corp., saunanius, USA;
copolyoxymethylene resin C: brand POM MC90, unblocked, melt index 9 g/10min (190 ℃/2.16 KG), kai-Longyu chemical Co., ltd;
homo-formaldehyde resin: the brand is POM 500P, and the melt index is 14 g/10min (190 ℃/2.16 KG), duPont company, U.S.
Polyethyleneimine a: the molar percentage of primary amine to the sum of amine groups is 37mol%, brand Lupasol G100, germany BASF;
polyethyleneimine B: the molar percentage of primary amine in the sum of amine groups is 40mol%, with the trade name of Lupasol PR8515, germany BASF;
polyethyleneimine C: the mole percentage of primary amine accounting for the total amino groups is 50-60mol%, and the brand Lupasol SK, germany BASF;
polyethyleneimine D: the mole percent of primary amine accounting for the total amino groups is more than 90mol percent, and the brand Lupasol NW3 and Germany BASF;
polyethyleneimine E: the mole percent of primary amine to the sum of amine groups is 35.7 mole percent, brand Lupasol WF, german BASF;
an antioxidant: triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] and N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 1: 1.
Preparation method of polyoxymethylene compositions of examples and comparative examples: uniformly mixing the components according to the proportion, and extruding and granulating by a double-screw extruder to obtain the polyoxymethylene composition, wherein the screw temperature range is that the extruder is 180-190 ℃ in the first region, 180-190 ℃ in the second region, 180-190 ℃ in the third region, 180-190 ℃ in the fourth region, 190-200 ℃ in the fifth region, 190-200 ℃ in the sixth region, 190-200 ℃ in the seventh region, 190-200 ℃ in the eighth region and 190-200 ℃ in the ninth region; the rotation speed of the host machine is 250-400 rpm.
The testing method comprises the following steps:
(1) Formaldehyde release amount: the determination was performed according to the VDA 275 test standard, as follows: the polyoxymethylene resin was injection molded at 190-200 ℃ into square plates with 100mm x 2mm injection molded dimensions, then cut into square plates with 100mm x 40mm x 2mm dimensions, the injection molded sample was fixed in a 1 liter polyethylene bottle containing 50ml distilled water, the article was kept free from contact with water, the bottle was sealed, and the bottle was baked in an oven at 60 ℃ 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.
(2) Tensile creep test: the test was conducted according to ASTM D2990, and the test piece was 168mm by 13mm by 3.2mm in spline size, and the creep resistance was judged to be good by the time to reach 10% strain at 90℃and was better as the time was longer. The initial load was 25MPa.
Table 1: examples 1-6 polyoxymethylene compositions each component content (parts by weight) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Copolyoxymethylene resin A | 100 | 100 | 100 | 100 | ||
| Copolyoxymethylene resin B | 100 | |||||
| Copolyoxymethylene resin C | 100 | |||||
| Polyethyleneimine A | 2.7 | 2.7 | 2.7 | |||
| Polyethylene imine B | 2.7 | |||||
| Polyethyleneimine C | 2.7 | |||||
| Polyethyleneimine D | 2.7 | |||||
| Formaldehyde emission mg/kg | 1.50 | 1.62 | 2.19 | 1.33 | 1.10 | 0.82 |
| Tensile creep test, hours | 0.43 | 0.41 | 0.40 | 0.57 | 0.69 | 0.75 |
From examples 1 to 3, it was found that the amount of formaldehyde released by capping the copolyformaldehyde resin was further reduced.
From examples 1/4/5/6, it is clear that the molar percentage of primary amine in the polyethyleneimine, based on the sum of amine groups, significantly influences the inhibition of formaldehyde emission and creep resistance.
Table 2: examples 7-13 polyoxymethylene compositions each component content (parts by weight) and test results
| Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | |
| Copolyoxymethylene resin A | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Polyethylene imine B | 1.5 | 1.9 | 2.8 | 3 | 3.5 | 5 | 1.5 |
| Antioxidant | 0.2 | ||||||
| Formaldehyde emission mg/kg | 2.07 | 1.60 | 1.27 | 1.18 | 0.82 | 0.61 | 2.00 |
| Tensile creep test, hours | 0.45 | 0.51 | 0.60 | 0.57 | 0.50 | 0.42 | 0.42 |
As is clear from examples 4/7 to 12, the content of polyethyleneimine is preferably in the range of 1.9 to 3.5, more preferably 2.7 to 3, the creep resistance is better, and the formaldehyde emission amount can be suppressed to 2.0mg/kg or less.
Table 3: comparative example polyoxymethylene composition content (parts by weight) of each component and test result
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Copolyoxymethylene resin A | 100 | 100 | 100 | 100 | |
| Homo-polyoxymethylene resin | 100 | ||||
| Polyethyleneimine A | 1.5 | 6 | 0.5 | ||
| Polyethyleneimine E | 1.5 | ||||
| Antioxidant | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Formaldehyde emission mg/kg | 3.94 | 3.02 | 0.42 | 3.18 | 4.98 |
| Tensile creep test, hours | 0.35 | 0.29 | 0.35 | 0.31 | 0.23 |
As is clear from comparative example 1, the formaldehyde emission amount of the homo-formaldehyde resin was too high.
As is clear from comparative example 2, when the primary amine of polyethyleneimine is less than 37% by mole based on the total amine groups, the suppression of formaldehyde emission and the improvement of tensile creep are insufficient.
As is clear from comparative examples 3/4, when the amount of polyethyleneimine added is too high, although the formaldehyde emission can be further suppressed, the creep resistance is also much reduced, less than 0.4 hours; when the amount of polyethyleneimine added is too low, the formaldehyde emission is high.
Claims (11)
1. The polyoxymethylene composition is characterized by comprising the following components in parts by weight:
100 parts of copolymerized formaldehyde resin;
1.5-5 parts of polyethyleneimine;
wherein the mole percentage of primary amine in the polyethyleneimine accounting for the sum of amino groups is more than or equal to 37mol percent.
2. Polyoxymethylene composition according to claim 1, wherein the polyethylene imine is 1.9-3.5 parts.
3. Polyoxymethylene composition according to claim 2, wherein the polyethylenimine is 2.7-3 parts.
4. The polyoxymethylene composition of claim 1, wherein the primary amine in the polyethyleneimine is at least 40 mole percent of the total amine groups.
5. The polyoxymethylene composition of claim 4, wherein the primary amine in the polyethyleneimine is at least 50 mole% of the total amine groups.
6. The polyoxymethylene composition of claim 5, wherein the primary amine in the polyethyleneimine is at least 90 mole percent based on the total amine groups.
7. The polyoxymethylene composition of claim 1, wherein the copolyformaldehyde resin has a melt index in the range of 0.5 to 300g/10min under test conditions of 190 ℃/2.16KG.
8. The polyoxymethylene composition of claim 1, wherein the copolyformaldehyde resin is end-capped.
9. The polyoxymethylene composition of claim 1, further comprising 0 to 1 part by weight of an antioxidant.
10. A process for the preparation of a polyoxymethylene composition as set forth in any one of claims 1 to 9, which comprises the steps of: according to the proportion, the components are evenly mixed and extruded and granulated by a double-screw extruder to obtain the polyoxymethylene composition, wherein the temperature range of the screw is 180-200 ℃ and the rotating speed is 250-400 rpm.
11. Use of the polyoxymethylene composition of any one of claims 1 to 9, for gears, sliding elements, screws, nuts, pump parts, valve bodies.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07207118A (en) * | 1994-01-12 | 1995-08-08 | Polyplastics Co | Polyoxymethylene composition |
| JPH1135791A (en) * | 1997-07-14 | 1999-02-09 | Sanyo Chem Ind Ltd | Oxymethylene (co)polymer composition |
| CN1518577A (en) * | 2001-06-19 | 2004-08-04 | �����ɷ� | Stabilised thermoplastic moulding compounds |
| DE102004008722A1 (en) * | 2004-02-23 | 2005-09-08 | Ticona Gmbh | Composition for molding, comprising polyoxymethylene polymer and ester or amide wax, emits reduced emission of formaldehyde during preparation and processing |
| WO2006120199A1 (en) * | 2005-05-10 | 2006-11-16 | Basf Aktiengesellschaft | Use of polyethylene imines for reducing the residual formaldehyde content of polyoxymethylenes |
| WO2006120218A1 (en) * | 2005-05-11 | 2006-11-16 | Basf Aktiengesellschaft | Improved method for removal of residual monomer from polyoxymethylenes |
| WO2011128437A1 (en) * | 2010-04-16 | 2011-10-20 | Basf Se | Highly branched amine polymers and amine oligomers as corrosion inhibitor |
-
2021
- 2021-12-15 CN CN202111531793.6A patent/CN114685932B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07207118A (en) * | 1994-01-12 | 1995-08-08 | Polyplastics Co | Polyoxymethylene composition |
| JPH1135791A (en) * | 1997-07-14 | 1999-02-09 | Sanyo Chem Ind Ltd | Oxymethylene (co)polymer composition |
| CN1518577A (en) * | 2001-06-19 | 2004-08-04 | �����ɷ� | Stabilised thermoplastic moulding compounds |
| DE102004008722A1 (en) * | 2004-02-23 | 2005-09-08 | Ticona Gmbh | Composition for molding, comprising polyoxymethylene polymer and ester or amide wax, emits reduced emission of formaldehyde during preparation and processing |
| WO2006120199A1 (en) * | 2005-05-10 | 2006-11-16 | Basf Aktiengesellschaft | Use of polyethylene imines for reducing the residual formaldehyde content of polyoxymethylenes |
| WO2006120218A1 (en) * | 2005-05-11 | 2006-11-16 | Basf Aktiengesellschaft | Improved method for removal of residual monomer from polyoxymethylenes |
| WO2011128437A1 (en) * | 2010-04-16 | 2011-10-20 | Basf Se | Highly branched amine polymers and amine oligomers as corrosion inhibitor |
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