CN1594423A - Polyformaldehyde/thermoplastic polyurethane elastomer blends and their preparation process and use - Google Patents
Polyformaldehyde/thermoplastic polyurethane elastomer blends and their preparation process and use Download PDFInfo
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- CN1594423A CN1594423A CN 200410040158 CN200410040158A CN1594423A CN 1594423 A CN1594423 A CN 1594423A CN 200410040158 CN200410040158 CN 200410040158 CN 200410040158 A CN200410040158 A CN 200410040158A CN 1594423 A CN1594423 A CN 1594423A
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- polyoxymethylene
- thermoplastic polyurethane
- ethylene
- polyurethane elastomer
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Abstract
The invention discloses a modified polyformaldehyde/ thermoplastic polyaminoester elastomer blend, its preparation method and use thereof, wherein the preparation method consists of charging polyformaldehyde 70-85 weight parts, thermoplastic urethane elastomer 30-15 weight parts, compatibilizer 4-20 weight parts, lubricating agent 0.2-1.5 weight parts into high speed mixing machine, mixing uniformly, granulating with a double bolt extrusion machine, then subjecting the cross blend to injection moulding with an injection machine.
Description
One, technical field
The present invention relates to a kind of polyoxymethylene/thermoplastic polyurethane elastomer blended thing and its production and use, belong to polymer processing field.
Two, background technology
Polyoxymethylene is a kind of engineering plastics with excellent comprehensive performance, since du pont company is at first realized industrialization from nineteen fifty-nine, polyoxymethylene is just cheap and easy to get with its raw material, machine-shaping is convenient, particularly special mechanical properties, oil-proofness, chemical resistant properties, low water absorbable and good heat, electrical property, and be used to replace non-ferrous metal and alloy, be widely used in automobile, electronic apparatus industry, generally reach industries such as precision optical machinery and five metals building materials, as component such as bearing, gear, automobile instrument spare, pump leaf impellers.At present, in whole THE ENGINEERING PLASTICS INDUSTRY, the annual production of polyoxymethylene is only second to nylon and polycarbonate, occupies the 3rd, is one of the world today's five large-engineering plastics.
Polyoxymethylene is a kind of unbranched line polymer, and molecular chain structure is simply regular, and crystallization velocity and higher degree of crystallinity (general degree of crystallinity can reach more than 60%) are faster arranged, and be easy to form big spherulitic crystal structure, thereby toughness is relatively poor, and notched Izod impact strength is low; The goods shrinking percentage is big in the moulding process, is difficult to precise forming, and this and its excellent comprehensive performances is not complementary, and has limited the application of polyoxymethylene in every field.Therefore its toughening modifying becomes the problem that people pay close attention to already.Because the structural characteristics of polyoxymethylene, its surface tension is higher, and is very poor with other polymer phase capacitive, and this also is a polyoxymethylene blending material major cause of less types.
Chinese patent 99813932.7 is disclosed to be the polyoxymethylene resin composition of extensibility, thermostability and impact strength with raising, and it is the polyformaldehyde resin by 50～97% weight; The thermoplastic polyester elastomer of 3～50% weight is as necessary elastomeric component and the optional elastomeric component of Polyurethane Thermoplastic Elastomer conduct; And the maleic anhydride grafted polymer of 0.1～10% weight.Disclosure by this patent is learnt, adds after the maleic anhydride grafted polymer in polyoxymethylene/polyester elastomer composition, and composition elongation increased value is 45%, and shock strength does not increase; Add after the maleic anhydride grafted polymer in polyoxymethylene/polyester elastomer/polyurethane elastomeric compositions, composition elongation increased value is 80%, and the shock strength increasing degree is 13%.
United States Patent (USP) 4804716 disclosed toughening polyoxymethylene compositions are made up of the polyoxymethylene of 60～85% weight parts and the Polyurethane Thermoplastic Elastomer of 15～40% weight parts, and the Izod notched Izod impact strength value of composition surpasses 375J/m.But do not mention the tensile strength and the tension fracture elongation rate of composition in the patent.
Chinese patent 90109363.7 is disclosed to be polyoxymethylene/Polyurethane Thermoplastic Elastomer/amorphous thermoplastic polymer blend composition, and this blend composition is made up of the polyoxymethylene of 40～98% weight, the Polyurethane Thermoplastic Elastomer of 1～40% weight and at least a amorphous thermoplastic polymer of 1～59% weight.Disclosure by this patent learns that the elongation of this blend composition is lower.
Three, summary of the invention
The objective of the invention is provides a kind of polyoxymethylene/thermoplastic polyurethane elastomer blended thing and its production and use at the deficiencies in the prior art, be characterized in polyoxymethylene/thermoplastic polyurethane elastomer blended modifier thing, adding expanding material and lubricant, the shock strength of polyoxymethylene/thermoplastic polyurethane elastomer blended thing and elongation at break are further enhanced.
Purpose of the present invention adopts following technical measures to realize that wherein said raw material umber is parts by weight except that specified otherwise.
The recipe ingredient of polyoxymethylene/thermoplastic polyurethane elastomer blended modifier thing is: 0.2～1.5 part of 70～85 parts of polyoxymethylene, 30～15 parts of Polyurethane Thermoplastic Elastomer, 4～10 parts of expanding materials and lubricant.
Expanding material is any in ethylene-vinyl acetate copolymer (EVA), ethylene/ethyl acrylate multipolymer (EEA) and the ethylene-acrylic acid copolymer (EAA).
Lubricant is any in the two amine hydroxybenzenes of ethylene bis stearic amide, ethylene, Zinic stearas and the calcium stearate.
The preparation method of polyoxymethylene/thermoplastic polyurethane elastomer blended modifier thing:
With 0.2～1.5 part of 70～85 parts of starting raw material polyoxymethylene, 30～15 parts of Polyurethane Thermoplastic Elastomer, 4～10 parts of expanding materials and lubricant, add and mix back parallel dual-screw extruding machine granulation in the high-speed mixer, each section of forcing machine temperature is respectively 180～190 ℃, 195～205 ℃, 195～205 ℃, 195～205 ℃, 195～200 ℃ of head temperatures.Through the blend injection moulding machine injection moulding of forcing machine granulation, each section of injection moulding machine temperature is 50～70 ℃, 170～180 ℃, and 190～200 ℃, 195～205 ℃ and 195～205 ℃.
The polyoxymethylene that makes/thermoplastic polyurethane elastomer blended modifier thing has excellent comprehensive performances, detailed being shown in Table 1, the tension fracture elongation rate of the polyoxymethylene after modification of the present invention/thermoplastic polyurethane elastomer blended thing brings up to 425% by 91%, and notched Izod impact strength is by 17.4kJ/m
2Bring up to 24.2kJ/m
2
Blended modifier of the present invention can be used in the fields such as automobile, household electrical appliances, daily life.
The present invention has following advantage: technology is simple, and is easy and simple to handle, and cost is lower, and the polyoxymethylene that makes/thermoplastic polyurethane elastomer blended modifier thing has excellent comprehensive performances.
Four, embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to foregoing.
Embodiment:
1, with polyoxymethylene 80kg, Polyurethane Thermoplastic Elastomer 20kg, ethylene-acrylic acid copolymer 6kg and ethylene bis stearic amide 0.5kg, add high-speed mixer and mix back twin screw extruder extruding pelletization, each section of forcing machine temperature is respectively 185 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ of head temperatures.Through the blend injection moulding machine injection moulding of forcing machine granulation, each section of injection moulding machine temperature is 50 ℃, 170 ℃, and 190 ℃, 195 ℃ and 195 ℃.
2, with the two amine hydroxybenzene 0.8kg of polyoxymethylene 75kg, Polyurethane Thermoplastic Elastomer 25kg, ethylene-vinyl acetate copolymer 4kg and ethylene, add high-speed mixer and mix back twin screw extruder extruding pelletization, each section of forcing machine temperature is respectively 190 ℃, 198 ℃, 198 ℃, 198 ℃, 196 ℃ of head temperatures.Through the blend injection moulding machine injection moulding of forcing machine granulation, each section of injection moulding machine temperature is 50 ℃, 180 ℃, and 195 ℃, 195 ℃ and 200 ℃.
3, with polyoxymethylene 84kg, Polyurethane Thermoplastic Elastomer 16kg, ethylene/ethyl acrylate multipolymer 8kg and Zinic stearas 0.3kg, add high-speed mixer and mix back twin screw extruder extruding pelletization, each section of forcing machine temperature is respectively 190 ℃, 195 ℃, 200 ℃, 200 ℃, 198 ℃ of head temperatures.Through the blend injection moulding machine injection moulding of forcing machine granulation, each section of injection moulding machine temperature is 60 ℃, 180 ℃, and 190 ℃, 200 ℃ and 200 ℃.
The comparison of table 1 blended modifier of the present invention and prior art material resources performance
Tensile strength elongation at break simply supported beam notched Izod impact strength
Sample
(MPa) (％) (kJ/m
2)
Polyoxymethylene 60.1 46 7.2
Unmodified polyoxymethylene/thermoplastic poly
38.3 91 17.4
The ammonia ester elastomer
Modification 1 34.5 221 19.5 of the present invention
Modification 2 33.9 327 23.3 of the present invention
Modification 3 34.5 425 24.2 of the present invention
Claims (5)
1. polyoxymethylene/thermoplastic polyurethane elastomer blended thing is characterized in that the recipe ingredient of this blend is by weight:
70～85 parts of polyoxymethylene
30～15 parts of Polyurethane Thermoplastic Elastomer
4～10 parts of expanding materials
0.2～1.5 part of lubricant
The elongation at break of this blend is 425%, and notched Izod impact strength is 24.2kJ/m
2
2. polyoxymethylene/thermoplastic polyurethane elastomer blended thing according to claim 1 is characterized in that expanding material is any in ethylene-vinyl acetate copolymer, ethylene/ethyl acrylate multipolymer and the ethylene-acrylic acid copolymer.
3. polyoxymethylene/thermoplastic polyurethane elastomer blended thing as claimed in claim 1 or 2 is characterized in that lubricant is any in the two amine hydroxybenzenes of ethylene bis stearic amide, ethylene, Zinic stearas and the calcium stearate.
4. as the preparation method of polyoxymethylene/thermoplastic polyurethane elastomer blended thing as described in the claim 1～3, it is characterized in that:
1) with starting raw material polyoxymethylene 70～85 weight parts, Polyurethane Thermoplastic Elastomer 30～15 weight parts, expanding material 4～10 weight parts, lubricant 0.2～1.5 weight part, add and mix back parallel dual-screw extruding machine granulation in the high-speed mixer, each section of forcing machine temperature is respectively 180～190 ℃, 195～205 ℃, 195～205 ℃, 195～205 ℃, 195～200 ℃ of head temperatures.
2) through the blend injection moulding machine injection moulding of forcing machine granulation, each section of injection moulding machine temperature is 50～70 ℃, 170～180 ℃, and 190～200 ℃, 195～205 ℃ and 195～205 ℃.
5. as the purposes of polyoxymethylene/thermoplastic polyurethane elastomer blended thing as described in the claim 1～4, it is characterized in that this blend is mainly used in automobile, household electrical appliances and daily life field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410040158 CN1233733C (en) | 2004-07-09 | 2004-07-09 | Polyformaldehyde/thermoplastic polyurethane elastomer blends and their preparation process and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410040158 CN1233733C (en) | 2004-07-09 | 2004-07-09 | Polyformaldehyde/thermoplastic polyurethane elastomer blends and their preparation process and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1594423A true CN1594423A (en) | 2005-03-16 |
| CN1233733C CN1233733C (en) | 2005-12-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410040158 Expired - Fee Related CN1233733C (en) | 2004-07-09 | 2004-07-09 | Polyformaldehyde/thermoplastic polyurethane elastomer blends and their preparation process and use |
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| CN (1) | CN1233733C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381017B (en) * | 2008-08-05 | 2010-06-09 | 江苏明昊新材料科技有限公司 | Silica gel tank material and method for producing silica gel tank and silica gel tank obtained therefrom |
| CN102095027A (en) * | 2010-09-24 | 2011-06-15 | 天津鹏翎胶管股份有限公司 | Fuel tank drainage pipe for automobile and preparation method of pipe |
| CN102391605A (en) * | 2011-09-02 | 2012-03-28 | 沈阳科通塑胶有限公司 | Preparation method of polyformaldehyde toughening agent, toughening polyformaldehyde and toughening agent |
| CN105295293A (en) * | 2015-10-09 | 2016-02-03 | 上海克络蒂材料科技发展有限公司 | Connector material for door and window profiles and preparation method thereof |
| CN105694344A (en) * | 2016-01-29 | 2016-06-22 | 宁波海飞电器有限公司 | Plastic alloy for washing machine cover plate and preparation method of plastic alloy |
| CN106147115A (en) * | 2016-07-01 | 2016-11-23 | 古道尔工程塑胶（深圳）有限公司 | A kind of POM/TPU antimicrobial composite material and preparation method thereof |
| CN112795132A (en) * | 2021-01-07 | 2021-05-14 | 金发科技股份有限公司 | Polyformaldehyde composition and preparation method thereof |
| CN113831680A (en) * | 2020-06-24 | 2021-12-24 | 合肥杰事杰新材料股份有限公司 | Low-shrinkage high-toughness polyformaldehyde composition and preparation method thereof |
-
2004
- 2004-07-09 CN CN 200410040158 patent/CN1233733C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381017B (en) * | 2008-08-05 | 2010-06-09 | 江苏明昊新材料科技有限公司 | Silica gel tank material and method for producing silica gel tank and silica gel tank obtained therefrom |
| CN102095027A (en) * | 2010-09-24 | 2011-06-15 | 天津鹏翎胶管股份有限公司 | Fuel tank drainage pipe for automobile and preparation method of pipe |
| CN102391605A (en) * | 2011-09-02 | 2012-03-28 | 沈阳科通塑胶有限公司 | Preparation method of polyformaldehyde toughening agent, toughening polyformaldehyde and toughening agent |
| CN102391605B (en) * | 2011-09-02 | 2012-10-24 | 沈阳科通塑胶有限公司 | Preparation method of polyformaldehyde toughening agent, toughening polyformaldehyde and toughening agent |
| CN105295293A (en) * | 2015-10-09 | 2016-02-03 | 上海克络蒂材料科技发展有限公司 | Connector material for door and window profiles and preparation method thereof |
| CN105694344A (en) * | 2016-01-29 | 2016-06-22 | 宁波海飞电器有限公司 | Plastic alloy for washing machine cover plate and preparation method of plastic alloy |
| CN105694344B (en) * | 2016-01-29 | 2018-04-13 | 宁波海飞电器有限公司 | A kind of cover plate for washing machine plastic alloy and preparation method thereof |
| CN106147115A (en) * | 2016-07-01 | 2016-11-23 | 古道尔工程塑胶（深圳）有限公司 | A kind of POM/TPU antimicrobial composite material and preparation method thereof |
| CN113831680A (en) * | 2020-06-24 | 2021-12-24 | 合肥杰事杰新材料股份有限公司 | Low-shrinkage high-toughness polyformaldehyde composition and preparation method thereof |
| CN112795132A (en) * | 2021-01-07 | 2021-05-14 | 金发科技股份有限公司 | Polyformaldehyde composition and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1233733C (en) | 2005-12-28 |
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Owner name: SICHUAN UNIVERSITY Effective date: 20050218 Owner name: YUNNAN YUNTIANHUA CO., LTD. Free format text: FORMER OWNER: SICHUAN UNIVERSITY |
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Effective date of registration: 20050218 Address after: Yunnan province is rich Applicant after: Yutianhua Co., Ltd., Yunnan Co-applicant after: Sichuan University Address before: Sichuan city of Chengdu province moziqiao Applicant before: Sichuan University |
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Granted publication date: 20051228 Termination date: 20130709 |