CN104231208A - Recycled carbon fiber enhanced TPU (thermoplastic polyurethane) elastomer and preparation method thereof - Google Patents
Recycled carbon fiber enhanced TPU (thermoplastic polyurethane) elastomer and preparation method thereof Download PDFInfo
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- CN104231208A CN104231208A CN201410479981.2A CN201410479981A CN104231208A CN 104231208 A CN104231208 A CN 104231208A CN 201410479981 A CN201410479981 A CN 201410479981A CN 104231208 A CN104231208 A CN 104231208A
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- thermoplastic elastomer
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- polyurethane thermoplastic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4283—Hydroxycarboxylic acid or ester
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a recycled carbon fiber enhanced TPU (thermoplastic polyurethane) elastomer and a preparation method thereof. The TPU elastomer comprises ingredients in parts by weight as follows: 40-60 parts of polyester polyol, 35-58 parts of diisocyanate, 2-7 parts of recycled carbon fiber and 13-23 parts of a chain extender, wherein polyester polyol, diisocyanate and the recycled carbon fiber are subjected to prepolymerization according to a formula ratio; and the chain extender is added into obtained prepolymer, and the recycled carbon fiber enhanced TPU elastomer is obtained after vulcanization and aging. According to the recycled carbon fiber enhanced TPU elastomer and the preparation method, a specific amount of recycled carbon fiber is used for preparing the TPU elastomer, the mechanical property of the TPU elastomer can be enhanced, the tensile strength, the tearing strength, the elongation at break and the like of the recycled carbon fiber enhanced TPU elastomer are improved to a greater extent while compared with polyurethane elastomers without carbon fiber, and the heat resistance is also improved greatly.
Description
Technical field
The present invention relates to polyurethane elastomer preparing technical field, be specifically related to a kind of recovery fibre reinforced Polyurethane Thermoplastic Elastomer and preparation method thereof.
Background technology
Carbon fiber be a kind of carbon content higher than 90% inorganic polymer fiber, a series of excellent properties such as there is high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, antifatigue, creep resistance, thermal expansivity are little.Carbon fiber as a kind of high-strength light high performance material and be widely used in the industries such as space flight and aviation, automobile, building, railway, communication, medical devices.Universal along with " low-carbon (LC) " idea in a large amount of operation of type aircraft and automobile and daily life, the demand of carbon fiber increases considerably year by year.But widely using of carbon-fibre composite, also creates a large amount of scrap stock and dead meal, these scrap stock and dead meals etc., bring immense pressure to environment protection on the one hand; On the other hand, the high value carbon-fibre component contained in matrix material, if simply carry out the process such as burning, also can cause the waste of resource.Therefore, the recycling of carbon fiber is the market of a very attractive, and it is not only guide with economic impact, equally because it to receive the concern of national governments to the favourable influence of environment.
Polyurethane material is a kind of synthetic materials between rubber and plastics, there is the performance of a series of excellences such as high mechanical strength, unreactiveness, high abrasion, low-temperature performance, adhesive property and elasticity is good, but itself there is poor heat resistance, the defect that softening and heat decomposition temperature is low, along with the expansion of the development and apply of science and technology, enhancing modified must be carried out to urethane, improve its performance.Therefore, be devoted to develop mechanical property, Good Heat-resistance compound polyurethane material become the important topic of polyurethane field research.
Summary of the invention
The object of the present invention is to provide a kind of recovery fibre reinforced Polyurethane Thermoplastic Elastomer and preparation method thereof.
For reaching this object, the present invention by the following technical solutions:
A kind of recovery fibre reinforced Polyurethane Thermoplastic Elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
The parts by weight of described polyester polyol can select 40.02 ~ 59.8,43 ~ 56,46.8 ~ 54.2,49 ~ 51.5,50.6 etc., all can be used for implementing the present invention.
The parts by weight of described vulcabond can select 35.03 ~ 57.8,38 ~ 54,40.7 ~ 50,43 ~ 48.5,45 etc., all can be used for implementing the present invention.
The parts by weight of described recovery carbon fiber can select 2.01 ~ 6.8,2.3 ~ 6.4,3 ~ 6,3.4 ~ 5.1,4 ~ 4.7,4.3 etc., all can be used for implementing the present invention.
The parts by weight of described chainextender can select 13.02 ~ 22.8,15 ~ 21,16.4 ~ 20.4,17 ~ 19,18.4 etc., all can be used for implementing the present invention.
Along with reclaiming the increase of carbon fiber content, the tensile strength of polyurethane elastomer, tear strength and tensile yield are all first raise rear reduction.Wherein when the parts by weight reclaiming carbon fiber are 2 ~ 7, its mechanical property is optimum.This is because the increase of reclaiming carbon fiber content is equivalent to improve the concentration of hard section in polyurethane elastomer segment, thus improve its mechanical property.But along with reclaiming the increase of carbon fiber content, its dispersion difficulty in polyurethane elastomer increases, and also there occurs agglomeration, causes the decline of polyurethane elastomer performance.
Described polyester polyol is the mixture of a kind of in polyester adipate, poly-azelate, poly-butyric ester or polycarbonate or at least two kinds.Typical but non-limiting example includes but not limited to: polyester adipate, poly-azelate, poly-butyric ester, polycarbonate, polyester adipate and poly-azelate, poly-butyric ester and polycarbonate, polyester adipate, poly-azelate and poly-butyric ester, polyester adipate, poly-azelate, poly-butyric ester and polycarbonate etc.
Described vulcabond comprises tolylene diisocyanate, diphenylmethanediisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 3, the mixture of a kind of in 3 '-dimethyl-4,4-biphenyl diisocyanate, triphenylmethane triisocyanate or PPDI or at least two kinds.Typical but non-limiting example includes but not limited to: tolylene diisocyanate, diphenylmethanediisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, 3, 3 '-dimethyl-4, 4-biphenyl diisocyanate, xylylene diisocyanate and 3, 3 '-dimethyl-4, 4-biphenyl diisocyanate, triphenylmethane triisocyanate and PPDI, tolylene diisocyanate, diphenylmethanediisocyanate and 1, 5-naphthalene diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, PPDI and diphenylmethanediisocyanate etc., all can be used for implementing the present invention.
Described chainextender comprises following compound: OH-(CH
2)
x-OH, wherein x is the integer of 5 to 26.
The length of described recovery carbon fiber is 2 ~ 6mm, preferred 4mm.Such as can select 2.01 ~ 5.9mm, 2.3 ~ 5.2mm, 2.8 ~ 5mm, 3.2 ~ 4.7mm, 3.8 ~ 4.3mm, 4.1mm etc., all can be used for implementing the present invention.
As the preferred technical solution of the present invention, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Described chainextender comprises following compound: OH-(CH
2)
x-OH, wherein x is the integer of 8 to 14.
As the most preferred technical scheme of the present invention, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Described chainextender comprises following compound: OH-(CH
2)
10-OH.
" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described Polyurethane Thermoplastic Elastomer different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... composition ".
A described method for preparing thermoplastic polyurethane elastomer, said method comprising the steps of:
1) by formula ratio by polyester polyol and vulcabond and the pre-polymerization of recovery carbon fiber;
2) in the performed polymer obtained, add chainextender, through sulfuration, aging after be recycled fibre reinforced Polyurethane Thermoplastic Elastomer.
Compared with prior art scheme, the present invention has following beneficial effect:
The present invention by the recovery carbon fiber of certain content for the preparation of Polyurethane Thermoplastic Elastomer, its mechanical property can be strengthened, tensile strength, tear strength and tensile yield etc. all obtain larger growth relative to not adding the polyurethane elastomer reclaiming carbon fiber, and resistance toheat is also greatly improved.
In addition, utilize reclaim carbon fiber prepare Polyurethane Thermoplastic Elastomer can efficent use of resources, the feature of environmental protection is strong.
The present invention is described in more detail below.But following example is only simple and easy example of the present invention, and do not represent or limit the scope of the present invention, protection scope of the present invention is as the criterion with claims.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
A kind of recovery fibre reinforced Polyurethane Thermoplastic Elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Described chainextender is OH-(CH
2)
5-OH.
1) by formula ratio by polyester polyol and vulcabond and the pre-polymerization of recovery carbon fiber;
2) in the performed polymer obtained, add chainextender, through sulfuration, aging after be recycled fibre reinforced Polyurethane Thermoplastic Elastomer.
Embodiment 2
A kind of recovery fibre reinforced Polyurethane Thermoplastic Elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Described chainextender is OH-(CH
2)
26-OH.
Its preparation method is with embodiment 1.
Embodiment 3
A kind of recovery fibre reinforced Polyurethane Thermoplastic Elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Described chainextender is OH-(CH
2)
14-OH.
Its preparation method is with embodiment 1.
Embodiment 4
A kind of recovery fibre reinforced Polyurethane Thermoplastic Elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Described chainextender is OH-(CH
2)
8-OH.
Its preparation method is with embodiment 1.
Embodiment 5
A kind of recovery fibre reinforced Polyurethane Thermoplastic Elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Described chainextender is OH-(CH
2)
10-OH.
Its preparation method is with embodiment 1.
Compared the mechanical property of not adding the polyurethane elastomer reclaiming carbon fiber by the mechanical property of the recovery fibre reinforced Polyurethane Thermoplastic Elastomer prepared by the present invention and obtain larger enhancing, tensile strength increases by 25%, tear strength increases by 52%, and tensile yield increases by 8%.Reclaim carbon fiber serves activeness and quietness effect to Polyurethane Thermoplastic Elastomer.
Applicant states, person of ordinary skill in the field is on the basis of above-described embodiment, by the concrete content point value of above-described embodiment component, combined with the technical scheme of summary of the invention part, thus the new numerical range produced, also be one of record scope of the present invention, the application, for making specification sheets simple and clear, no longer enumerates these numerical ranges.
Applicant states, the present invention illustrates of the present invention by above-described embodiment, but the present invention is not limited to aforesaid operations step, does not namely mean that the present invention must rely on aforesaid operations step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (8)
1. reclaim a fibre reinforced Polyurethane Thermoplastic Elastomer, it is characterized in that, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
2. Polyurethane Thermoplastic Elastomer as claimed in claim 1, is characterized in that, described polyester polyol is the mixture of a kind of in polyester adipate, poly-azelate, poly-butyric ester or polycarbonate or at least two kinds.
3. Polyurethane Thermoplastic Elastomer as claimed in claim 1 or 2, it is characterized in that, described vulcabond comprises tolylene diisocyanate, diphenylmethanediisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 3, the mixture of a kind of in 3 '-dimethyl-4,4-biphenyl diisocyanate, triphenylmethane triisocyanate or PPDI or at least two kinds.
4. the Polyurethane Thermoplastic Elastomer as described in one of claim 1-3, is characterized in that, described chainextender comprises following compound: OH-(CH
2)
x-OH, wherein x is the integer of 5 to 26.
5. the Polyurethane Thermoplastic Elastomer as described in one of claim 1-4, is characterized in that, the length of described recovery carbon fiber is 2 ~ 6mm, preferred 4mm.
6. the Polyurethane Thermoplastic Elastomer as described in one of claim 1-5, is characterized in that, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Described chainextender comprises following compound: OH-(CH
2)
x-OH, wherein x is the integer of 8 to 14.
7. the Polyurethane Thermoplastic Elastomer as described in one of claim 1-6, is characterized in that, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Described chainextender comprises following compound: OH-(CH
2)
10-OH.
8. the method for preparing thermoplastic polyurethane elastomer as described in one of claim 1-7, is characterized in that, said method comprising the steps of:
1) by formula ratio by polyester polyol and vulcabond and the pre-polymerization of recovery carbon fiber;
2) in the performed polymer obtained, add chainextender, through sulfuration, aging after be recycled fibre reinforced Polyurethane Thermoplastic Elastomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410479981.2A CN104231208A (en) | 2014-09-18 | 2014-09-18 | Recycled carbon fiber enhanced TPU (thermoplastic polyurethane) elastomer and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410479981.2A CN104231208A (en) | 2014-09-18 | 2014-09-18 | Recycled carbon fiber enhanced TPU (thermoplastic polyurethane) elastomer and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804173A (en) * | 2015-05-18 | 2015-07-29 | 吴江市宏宇机械有限公司 | High-temperature-resistant polyurethane elastomer for mold resin and preparation method of polyurethane elastomer |
| CN106008898A (en) * | 2016-07-28 | 2016-10-12 | 东莞市吉鑫高分子科技有限公司 | High-moisture-resistance cold/heat-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN116333483A (en) * | 2023-05-12 | 2023-06-27 | 广东爱上新材料股份有限公司 | Anti-skid shock-absorbing polyurethane rubber particles for runway and preparation method thereof |
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| CN1966542A (en) * | 2006-06-23 | 2007-05-23 | 天津爱尼机电有限公司 | High-performance polyurethane elastomer and making method thereof |
| CN103012719A (en) * | 2012-12-13 | 2013-04-03 | 洛阳吉明化工有限公司 | Method for preparing polyurethane adhesive for high-temperature-resistant printing ink |
| CN103562249A (en) * | 2011-03-24 | 2014-02-05 | 拜耳知识产权有限责任公司 | Moulded parts consisting of reinforced polyurethane urea elastomers and use thereof |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966542A (en) * | 2006-06-23 | 2007-05-23 | 天津爱尼机电有限公司 | High-performance polyurethane elastomer and making method thereof |
| CN103562249A (en) * | 2011-03-24 | 2014-02-05 | 拜耳知识产权有限责任公司 | Moulded parts consisting of reinforced polyurethane urea elastomers and use thereof |
| CN103012719A (en) * | 2012-12-13 | 2013-04-03 | 洛阳吉明化工有限公司 | Method for preparing polyurethane adhesive for high-temperature-resistant printing ink |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804173A (en) * | 2015-05-18 | 2015-07-29 | 吴江市宏宇机械有限公司 | High-temperature-resistant polyurethane elastomer for mold resin and preparation method of polyurethane elastomer |
| CN104804173B (en) * | 2015-05-18 | 2017-10-17 | 吴江市宏宇机械有限公司 | It is a kind of resistant to elevated temperatures for polyurethane elastomer of resin mould and preparation method thereof |
| CN106008898A (en) * | 2016-07-28 | 2016-10-12 | 东莞市吉鑫高分子科技有限公司 | High-moisture-resistance cold/heat-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN116333483A (en) * | 2023-05-12 | 2023-06-27 | 广东爱上新材料股份有限公司 | Anti-skid shock-absorbing polyurethane rubber particles for runway and preparation method thereof |
| CN116333483B (en) * | 2023-05-12 | 2023-11-10 | 广东爱上新材料股份有限公司 | Anti-skid shock-absorbing polyurethane rubber particles for runway and preparation method thereof |
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