CN1844193A - Process of anion in-situ preparation of thermoplastic polyurethane and MC nylon 6 composite materials - Google Patents
Process of anion in-situ preparation of thermoplastic polyurethane and MC nylon 6 composite materials Download PDFInfo
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- CN1844193A CN1844193A CN 200610040170 CN200610040170A CN1844193A CN 1844193 A CN1844193 A CN 1844193A CN 200610040170 CN200610040170 CN 200610040170 CN 200610040170 A CN200610040170 A CN 200610040170A CN 1844193 A CN1844193 A CN 1844193A
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- polyurethane
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Abstract
The invention discloses an anionic in-situ method for preparation of thermoplastic polyurethane (TPU)/MC - nylon6 composite material. The raw materials include aminocaprolactam, TPU, accelerant, activating agent and so on. The method consists of heating and melting the aminocaprolactam first, then dewatering it in the vacuum, adding accelerant and continuing to dewater in the vacuum, then adding TPU raw material, magnetically stirring them to make TPU dissolve fully until it is adequately distributed in the aminocaprolactam flux, adding activating agent, after homogeneously mixed, casting them to a preheated die and demoulding to obtain the (TPU)/MC - nylon6 composite material. The dynamic ductility and the heat-proof quality of the composite material obtained by this method can be improved a lot on bases of the fundamental invariants of tensile strength and bending strength.
Description
Technical field
The present invention relates to adopt the anion in-situ polymerization to prepare thermoplastic polyurethane (TPU)/MC nylon 6 composite material, belong to materials science field.
Background technology
MC nylon 6 is a kind of in the nylon material, its preparation method is with fused hexanolactam decompression dehydration under normal pressure, and add strong alkaline substance and make catalyzer further after the dehydration, be mixed with activator auxiliary agents such as (as isocyanic ester), directly be injected in the mould of preheating certain temperature, material carries out the rapid polymerization reaction in mould, be frozen into solid blank.MC nylon has excellent mechanical property and advantages such as wear-resisting, anti-solvent, oil resistant, is widely used in fields such as mechanical component, weaving, petrochemical complex, national defense industry.In recent years, the main developing direction of macromolecular material is a high performance more and more, and MC nylon is compared with the Other Engineering plastics, and it is poor to exist shock resistance, and particularly under drying regime, MC nylon foundry goods is more crisp, and this has limited the range of application of MC nylon greatly.
Summary of the invention
The object of the present invention is to provide the anion in situ preparation method of a kind of thermoplastic polyurethane/MC nylon 6 composite material, the matrix material by the preparation of this method has increased substantially its shock resistance on the basis that keeps original MC nylon premium properties.
Technical scheme of the present invention is such, and the anion in situ preparation method of thermoplastic polyurethane/MC nylon 6 composite material is realized through the following steps:
The first step is heated to 100-120 ℃ with caprolactam monomer in reaction vessel, make material melting, vacuum hydro-extraction, and vacuum tightness is 10
-1-10
-3Pa adds catalyzer, continues vacuum hydro-extraction, and wherein, the weight ratio of catalyzer and caprolactam monomer is 0.1-2: 100;
Second step, remove vacuum, weight ratio according to Polyurethane Thermoplastic Elastomer and caprolactam monomer is 0-20: 100 ratio adds Polyurethane Thermoplastic Elastomer, be warming up to 150 ℃-170 ℃, magnetic agitation is fully dissolved until homodisperse Polyurethane Thermoplastic Elastomer in the hexanolactam melt, make homodisperse Polyurethane Thermoplastic Elastomer/hexanolactam melt, vacuum hydro-extraction, vacuum tightness are 10
-1-10
-3Pa;
The 3rd step, weight ratio according to activator and caprolactam monomer is 0-1.0: 100 ratio adds activator in Polyurethane Thermoplastic Elastomer/hexanolactam melt, be cast in the mould that is preheated to 150-180 ℃ after mixing rapidly, insulation 30min-1h postcooling promptly gets thermoplastic polyurethane of the present invention (TPU)/MC nylon 6 composite material.
Above-mentioned Polyurethane Thermoplastic Elastomer is the mixture of one or more Polyurethane Thermoplastic Elastomer class materials.
Above-mentioned Polyurethane Thermoplastic Elastomer class material comprises polyether-type and polyester type, and its hard section is various isocyanic ester (HDI/MDI/NDI), and soft section is all kinds of polymer polyatomic alcohols.
Above-mentioned catalyzer is a kind of in sodium Metal 99.5, potassium metal, metallic lithium, sodium hydroxide, potassium hydroxide, yellow soda ash, all kinds of organometallic compound.
Above-mentioned activator is a kind of in various isocyanic ester, ethanoyl hexanolactam, carbonic ether, the carboxylicesters.
Adopting rubber toughened MC nylon is to improve its flexible effective ways, and the present invention's usefulness has the Polyurethane Thermoplastic Elastomer toughened MC nylon of excellent impact resistance energy, has improved the shock resistance of MC nylon greatly, is expected to expand the range of application of MC nylon.The activator that adds among the present invention can effectively improve speed of response, and polyreaction is finished at short notice.The tensile strength of the matrix material by this law preparation is 65-80MPa, bending elastic modulus 600-1500MPa, notched Izod impact strength 10-20KJ/m
2, heat-resisting decomposition temperature has improved 20-50 ℃ than pure MC.
Embodiment
Following embodiment further specifies of the present invention, but not limits the scope of the invention.
The anion in situ preparation method of thermoplastic polyurethane of the present invention/MC nylon 6 composite material, realize through the following steps:
The first step places reaction vessel to be heated to 110 ℃ the hexanolactam of 100 weight parts, vacuum hydro-extraction 30min, and vacuum is 10
-1-10
-3Pa adds 0.40 weight part catalyzer sodium hydroxide, continues vacuum hydro-extraction 30min.
Second step, open valve, remove vacuum, the Polyurethane Thermoplastic Elastomer (the polyether-type 85s of trade mark Bayer company) that adds 3 weight parts, be warming up to 150 ℃, magnetic agitation is fully dissolved until homodisperse Polyurethane Thermoplastic Elastomer in the hexanolactam melt, vacuum hydro-extraction 30min, vacuum tightness is 10
-1-10
-3Pa.
The 3rd step, remove vacuum, add the activator 2.4-Xylene Diisocyanate of 0.65 weight part, be cast in the mould that is preheated to 150-180 ℃ after mixing rapidly, naturally cooling behind the insulation 1h promptly gets thermoplastic polyurethane (TPU)/MC nylon 6 composite material.
The matrix material that makes by the present embodiment method is through electron microscope observation, and TPU is with in the fibrous matrix that is dispersed in nylon, and its performance is as follows: tensile strength: 70MPa, bending elastic modulus: 1000Mpa, notched Izod impact strength 15KJ/m
2, the temperature of thermolysis 5% improves 30 ℃ than MC nylon.
Claims (6)
1, the anion in-situ polymerization process of thermoplastic polyurethane/MC nylon 6 composite material is characterized in that: realize through the following steps:
The first step is heated to 100-120 ℃ with caprolactam monomer in reaction vessel, make material melting, vacuum hydro-extraction, and vacuum tightness is 10
-1-10
-3Pa adds catalyzer, continues vacuum hydro-extraction, and wherein, the weight ratio of catalyzer and caprolactam monomer is 0.1-2: 100;
Second step, remove vacuum, weight ratio according to Polyurethane Thermoplastic Elastomer and caprolactam monomer is 0-20: 100 ratio adds Polyurethane Thermoplastic Elastomer, be warming up to 150 ℃-170 ℃, magnetic agitation is fully dissolved until homodisperse Polyurethane Thermoplastic Elastomer in the hexanolactam melt, make homodisperse Polyurethane Thermoplastic Elastomer/hexanolactam melt, vacuum hydro-extraction, vacuum tightness are 10
-1-10
-3Pa;
The 3rd step was cast to the second Polyurethane Thermoplastic Elastomer/hexanolactam melt that goes on foot gained in the mould that is preheated to 150-180 ℃, and insulation 30min-1h postcooling promptly gets thermoplastic polyurethane of the present invention/MC nylon 6 composite material.
2, the anion in-situ polymerization process of thermoplastic polyurethane according to claim 1/MC nylon 6 composite material, it is characterized in that: the weight ratio according to activator and caprolactam monomer in above-mentioned the 3rd step is 0-1.0: 100 ratio adds activator in Polyurethane Thermoplastic Elastomer/hexanolactam melt, cast after mixing rapidly again.
3, the anion in-situ polymerization process of thermoplastic polyurethane according to claim 1/MC nylon 6 composite material is characterized in that: above-mentioned Polyurethane Thermoplastic Elastomer is the mixture of one or more Polyurethane Thermoplastic Elastomer class materials.
4, the anion in-situ polymerization process of thermoplastic polyurethane according to claim 1/MC nylon 6 composite material, it is characterized in that: above-mentioned Polyurethane Thermoplastic Elastomer class material comprises polyether-type and polyester type, its hard section is various isocyanic ester, and soft section is all kinds of polymer polyatomic alcohols.
5, the anion in-situ polymerization process of thermoplastic polyurethane according to claim 1/MC nylon 6 composite material is characterized in that: above-mentioned catalyzer is a kind of in sodium Metal 99.5, potassium metal, metallic lithium, sodium hydroxide, potassium hydroxide, yellow soda ash, all kinds of organometallic compound.
6, the anion in-situ polymerization process of thermoplastic polyurethane according to claim 2/MC nylon 6 composite material is characterized in that: above-mentioned activator is a kind of in various isocyanic ester, ethanoyl hexanolactam, carbonic ether, the carboxylicesters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100401708A CN100404586C (en) | 2006-04-30 | 2006-04-30 | Process of anion in-situ preparation of thermoplastic polyurethane and MC nylon 6 composite materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100401708A CN100404586C (en) | 2006-04-30 | 2006-04-30 | Process of anion in-situ preparation of thermoplastic polyurethane and MC nylon 6 composite materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1844193A true CN1844193A (en) | 2006-10-11 |
| CN100404586C CN100404586C (en) | 2008-07-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100401708A Expired - Fee Related CN100404586C (en) | 2006-04-30 | 2006-04-30 | Process of anion in-situ preparation of thermoplastic polyurethane and MC nylon 6 composite materials |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100526383C (en) * | 2006-12-09 | 2009-08-12 | 中国科学院兰州化学物理研究所 | Method for producing polyurethane toughness-reinforcing cast form nylon composite material |
| CN102690413A (en) * | 2012-06-18 | 2012-09-26 | 河南省科学院高新技术研究中心 | Polyurethane modified nylon ball mill liner |
| CN103289381A (en) * | 2013-06-20 | 2013-09-11 | 四川大学 | In-situ reinforced and toughened MC nylon 6 composite material and preparation method thereof |
| CN103834163A (en) * | 2013-12-03 | 2014-06-04 | 广东科进尼龙管道制品有限公司 | Foam polyurethane-modified monomer casting (MC) nylon composite material and preparation method thereof |
| CN104339677A (en) * | 2013-08-07 | 2015-02-11 | 陕西华山胜邦塑胶有限公司 | Manufacturing method of nylon belt for armour-piercing bullet |
| WO2015114076A1 (en) * | 2014-01-31 | 2015-08-06 | Basf Se | Method for producing a thermoplastic copolymers from polycaprolactam and thermoplastic polyurethane |
| WO2015114073A1 (en) * | 2014-01-31 | 2015-08-06 | Basf Se | Method for producing a thermoplastic copolymer from polycaprolactam and thermoplastic polyurethane |
| CN105128371A (en) * | 2015-09-15 | 2015-12-09 | 安庆越球建筑防水材料有限公司 | Process for manufacturing roof waterproof coiled material |
| CN105273183A (en) * | 2015-11-20 | 2016-01-27 | 中南林业科技大学 | Composite friction material and preparation method and device thereof |
| CN105399947A (en) * | 2015-12-16 | 2016-03-16 | 江苏科技大学 | Reactive extrusion preparation method of polyamide 6-polyether polyurethane copolymer |
| CN105504265A (en) * | 2015-12-31 | 2016-04-20 | 华侨大学 | Anionic in-situ preparation method of reclaimed polyacrylonitrile fiber (R-PAN) in-situ-reinforced monomer cast (MC) nylon 6 composite material |
| CN105542151A (en) * | 2014-10-28 | 2016-05-04 | 株洲时代新材料科技股份有限公司 | Quincuncial elastic member and preparation method thereof |
| CN106947077A (en) * | 2017-03-24 | 2017-07-14 | 武汉纺织大学 | A kind of ultra-toughness MC nylon materials and preparation method thereof |
| CN107286630A (en) * | 2017-07-10 | 2017-10-24 | 上海沥高科技股份有限公司 | It is a kind of can fast sealing shaping flexible vacuum bag and preparation method thereof |
| CN111285993A (en) * | 2020-03-09 | 2020-06-16 | 江苏科技大学 | Preparation method of high-fluidity polyamide 6 elastomer |
| CN112175160A (en) * | 2020-10-14 | 2021-01-05 | 安徽宏翔农业机械有限公司 | Preparation method of high-strength clean agricultural ground roller adhesive |
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| JPS5912918A (en) * | 1982-07-13 | 1984-01-23 | Dainippon Ink & Chem Inc | Polyamide elastomer modified with urethane |
| NL8401843A (en) * | 1984-06-09 | 1986-01-02 | Stamicarbon | METHOD FOR PREPARING A POLYAMIDE |
| CN1257229C (en) * | 2004-09-30 | 2006-05-24 | 吉林大学 | Nylon/thermo plastic polyurethane alastic body alloy resin and its preparation method |
| CN100366679C (en) * | 2004-10-15 | 2008-02-06 | 吉林大学 | High impact-proof nylon alloy and production thereof |
-
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- 2006-04-30 CN CNB2006100401708A patent/CN100404586C/en not_active Expired - Fee Related
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100526383C (en) * | 2006-12-09 | 2009-08-12 | 中国科学院兰州化学物理研究所 | Method for producing polyurethane toughness-reinforcing cast form nylon composite material |
| CN102690413A (en) * | 2012-06-18 | 2012-09-26 | 河南省科学院高新技术研究中心 | Polyurethane modified nylon ball mill liner |
| CN103289381A (en) * | 2013-06-20 | 2013-09-11 | 四川大学 | In-situ reinforced and toughened MC nylon 6 composite material and preparation method thereof |
| CN103289381B (en) * | 2013-06-20 | 2015-04-22 | 四川大学 | In-situ reinforced and toughened MC nylon 6 composite material and preparation method thereof |
| CN104339677A (en) * | 2013-08-07 | 2015-02-11 | 陕西华山胜邦塑胶有限公司 | Manufacturing method of nylon belt for armour-piercing bullet |
| CN103834163A (en) * | 2013-12-03 | 2014-06-04 | 广东科进尼龙管道制品有限公司 | Foam polyurethane-modified monomer casting (MC) nylon composite material and preparation method thereof |
| WO2015114076A1 (en) * | 2014-01-31 | 2015-08-06 | Basf Se | Method for producing a thermoplastic copolymers from polycaprolactam and thermoplastic polyurethane |
| WO2015114073A1 (en) * | 2014-01-31 | 2015-08-06 | Basf Se | Method for producing a thermoplastic copolymer from polycaprolactam and thermoplastic polyurethane |
| CN106062025B (en) * | 2014-01-31 | 2020-04-17 | 巴斯夫欧洲公司 | Method for producing thermoplastic copolymers from polycaprolactam and thermoplastic polyurethane |
| CN106062025A (en) * | 2014-01-31 | 2016-10-26 | 巴斯夫欧洲公司 | Method for producing a thermoplastic copolymers from polycaprolactam and thermoplastic polyurethane |
| US10329374B2 (en) | 2014-01-31 | 2019-06-25 | Basf Se | Method for producing a thermoplastic copolymers from polycaprolactam and thermoplastic polyurethane |
| CN105542151B (en) * | 2014-10-28 | 2018-10-12 | 株洲时代新材料科技股份有限公司 | Plum blossom shape elastic element and preparation method thereof |
| CN105542151A (en) * | 2014-10-28 | 2016-05-04 | 株洲时代新材料科技股份有限公司 | Quincuncial elastic member and preparation method thereof |
| CN105128371A (en) * | 2015-09-15 | 2015-12-09 | 安庆越球建筑防水材料有限公司 | Process for manufacturing roof waterproof coiled material |
| CN105273183A (en) * | 2015-11-20 | 2016-01-27 | 中南林业科技大学 | Composite friction material and preparation method and device thereof |
| CN105399947A (en) * | 2015-12-16 | 2016-03-16 | 江苏科技大学 | Reactive extrusion preparation method of polyamide 6-polyether polyurethane copolymer |
| CN105504265A (en) * | 2015-12-31 | 2016-04-20 | 华侨大学 | Anionic in-situ preparation method of reclaimed polyacrylonitrile fiber (R-PAN) in-situ-reinforced monomer cast (MC) nylon 6 composite material |
| CN106947077A (en) * | 2017-03-24 | 2017-07-14 | 武汉纺织大学 | A kind of ultra-toughness MC nylon materials and preparation method thereof |
| CN107286630A (en) * | 2017-07-10 | 2017-10-24 | 上海沥高科技股份有限公司 | It is a kind of can fast sealing shaping flexible vacuum bag and preparation method thereof |
| CN111285993A (en) * | 2020-03-09 | 2020-06-16 | 江苏科技大学 | Preparation method of high-fluidity polyamide 6 elastomer |
| CN111285993B (en) * | 2020-03-09 | 2022-01-28 | 江苏科技大学 | Preparation method of high-fluidity polyamide 6 elastomer |
| CN112175160A (en) * | 2020-10-14 | 2021-01-05 | 安徽宏翔农业机械有限公司 | Preparation method of high-strength clean agricultural ground roller adhesive |
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| Publication number | Publication date |
|---|---|
| CN100404586C (en) | 2008-07-23 |
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Granted publication date: 20080723 Termination date: 20100430 |