CN101974219A - Wear-resistant anti-static polyurethane material and preparation method thereof - Google Patents
Wear-resistant anti-static polyurethane material and preparation method thereof Download PDFInfo
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- CN101974219A CN101974219A CN 201010523187 CN201010523187A CN101974219A CN 101974219 A CN101974219 A CN 101974219A CN 201010523187 CN201010523187 CN 201010523187 CN 201010523187 A CN201010523187 A CN 201010523187A CN 101974219 A CN101974219 A CN 101974219A
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Abstract
The invention relates to a polymer material and a preparation method thereof, in particular to a preparation method of a wear-resistant anti-static polyurethane material and a shoe material prepared from the same. The wear-resistant anti-static polyurethane material is made from a raw material A and a raw material B by mixed pouring and is characterized in that: the raw material A comprises the following components in percentage by mass: 30 to 45% of polyalcohol, 3 to 9% of chain extender, 0.5 to 0.9% of catalyst, 0.05 to 0.2% of foaming agent, 0.05 to 0.1% of foam stabilizer, 0.5 to 1% of antioxidant and 1 to 10% of inorganic conductive powder; and the raw material B is 40 to 55% of isocyanate by mass. The process of manufacturing soles from the polyurethane material is simple and ensures high performance and no environmental pollution; particularly, the anti-static performance and wear-resisting property of the polyurethane soles are both considered; and compared with the polyurethane soles with anti-static agent, the anti-static performance suffers less influence from temperature and humidity.
Description
Technical field
The present invention relates to a kind of macromolecular material and preparation method thereof, particularly a kind of wear-resisting antistatic polyurethane material preparation method and the footwear material of making thereof.
Background technology
Microvoid polyurethane footwear material is to develop a kind of faster footwear synthetic resins, have soft, comfortable and easy to wear, warming, high resilience, anti-skidding, and machine-shaping is also fairly simple, be subjected to more and more people's favor.But because the insulativity of polyurethane material can produce accumulation of static electricity during friction, cause phenomenons such as dust suction, electron device puncture, electric shock, we need adopt antistatic treatment to improve its electroconductibility to polyurethane product.
Chinese patent CN200510109891.5 discloses a kind of by add the technical scheme that antistatic ingredient reaches anlistatig purpose in polyurethane stock solution, and the antistatic ingredient of interpolation comprises tetra-allkylammonium monoalkyl vitriol and at least a compound that at least one has the specific molecular formula.The advantage of this method is that the consistency of static inhibitor and polyurethane stock solution is good, does not need surface treatment, and toxicity is big, easily decomposition, antistatic property are subjected to humiture to influence shortcomings such as big but organic antistatic agents exists.
Chinese patent CN200780011270.0 discloses a kind of antistatic polyurethane, this urethane be with ionic liquid as anti static additive, though this ionic liquid performance is more stable, exist synthetic complicated, the problem that wear resistance is bad.
Chinese patent CN200810220010.0 discloses a kind of nano modified abrasion resistant polyurethane varnish, improve the anti-mechanical friction performance and the weather resistance of polyurethane lacquer by the Nano filling that adds 2-10%, this method comparison environmental protection and can play good decoration effect, but the static that produces can not eliminate friction the time.
So,, the invention provides the stable and reasonable polyurethane material of wear resistance of a kind of environmental protection, antistatic property at the problem of above-mentioned existence.
Summary of the invention
The present invention is directed to the wearing no resistance of antistatic polyurethane material of prior art, and the organic antistatic agents unstable properties, be subjected to defectives such as humiture influences greatly, not environmental protection, provide a kind of wear resistance good, and can discharge the polyurethane material of the static charge of human body generation effectively.
To achieve these goals, the invention provides a kind of wear-resisting antistatic polyurethane material, it mixes cast by raw material A and raw material B and forms, wherein said raw material A comprises that mass percent is the polyvalent alcohol of 30%-45%, the chainextender of 3%-9%, the catalyzer of 0.5%-0.9%, the whipping agent of 0.05%-0.2%, the surfactant of 0.05%-0.1%, the oxidation inhibitor of 0.5%-1%, and the inorganic conductive powder of 1%-10%; Described B material is that mass percent is the isocyanic ester of 40%-55%.Preferably, described polyvalent alcohol is polyether glycol or polyester polyol.Described isocyanic ester is diphenylmethanediisocyanate or hexamethylene diisocyanate.
Preferably, described chainextender is ethylene glycol, glycerol and 1, one or more in the 4-butyleneglycol; Described whipping agent is a water; Described surfactant is: one or more in oleic acid diethylamine, stearic acid diethanolamine and the dodecyl benzene disulfonic acid; Described oxidation inhibitor is 2, the 6-tertiary butyl-4-methylphenol.Described inorganic conductive powder is one or more in conductive titanate dioxide powder, conduction barium sulfate powder and the conductive mica powder.
Preferably, described catalyzer is the mixture of organic amine and organic tin; Described organic amine is one or more in triethylene diamine, triethylamine, Tributylamine, dimethyl benzyl amine and the five methyl diethylentriamine; Described organic tin is one or more in stannous octoate, tin acetate, stannous octoate, dibutyl tin laurate and the tin laurate.
Preferably, described inorganic conductive powder is coated with one deck hydrophobic nature coupling agent.
Further, described coupling agent is one or more in titanic acid ester, phosphoric acid ester, boric acid ester or the aluminic acid ester.
The present invention also provides a kind of preparation above-mentioned wear-resisting antistatic polyurethane preparation methods, and it comprises the steps to be prepared from:
(1) will prepare polyvalent alcohol and isocyanic ester and be placed in the baking oven respectively and toast, standby;
(2) add chainextender, catalyzer, whipping agent, surfactant, oxidation inhibitor and inorganic conductive powder in the polyvalent alcohol after above-mentioned baking, and mix formation A material;
(3) with A material and B material isocyanic ester mixing casting, make wear-resisting antistatic polyurethane material.
In order to improve the affinity of inorganic conductive powder and organic polymer, described inorganic conductive powder adopts coupling agent to coat pre-treatment.Make it become hydrophobic nature, thereby improve the interface bonding between conductive powder body and the polymkeric substance, improve the dispersion effect of inorganic conductive powder by wetting ability.Preferably, described inorganic conductive powder adopts coupling agent to carry out the coating pre-treatment of following steps:
A, with coupling agent and thinner according to the ratio dissolving of 1:5, mix;
B, the inorganic conductive powder added in the above-mentioned solution mix;
C, mixed inorganic conductive powder is put into vacuum drying oven baking finish the coating pre-treatment.
Preferably, the consumption of coupling agent is the 0.5-3% of inorganic conductive powder quality.
Preferably, described thinner is ethanol, toluene or dimethylbenzene.
Preferably, described coupling agent solution adopts ultrasonic wave to mix with the inorganic conductive powder.
The polyurethane electrostatic resistance sole that is made by aforesaid method specifically is to obtain by the following method:
(1) pre-treatment: with polyether glycol or polyester polyol, isocyanic ester is placed in the baking oven and dries by the fire 7-10h down at 70-80 ℃;
(2) batching: the inorganic conductive powder that various raw materials, auxiliary agent and coating is pretreated quantitatively carries out proportioning by prescription;
(3) casting: A material and B material are added A in the PU casting molding machine respectively, in the B charging basket, be heated to 40-45 ℃ of casting, the slaking of passing through 1-5 minute promptly gets at the bottom of the polyurethane shoe.
Provided by the present invention compared with prior art have a following advantage:
The complete processing that above-mentioned polyurethane material is made sole is simple, excellent performance, environmentally friendly, especially antistatic property and wear resisting property at the bottom of the polyurethane shoe have been taken into account, and because electro-conductive material is an inorganic materials, its antistatic property is subjected to the influence of humiture little with comparing at the bottom of the polyurethane shoe that adds static inhibitor, and environmentally friendly.
Specific embodiments
Below in conjunction with several specific embodiments, further specify wear-resisting antistatic polyurethane preparation methods provided by the present invention, and illustrate by the advantage of the resulting polyurethane material of preparation method provided by the present invention on antistatic property, wear resisting property in conjunction with existing conventional polyurethanes material.
Comparative example's (all components are all by percentage to the quality):
Its proportioning raw materials is as follows:
| The A material: | Polycarbonate polyol: | 42% |
| ? | 1, the 4-butyleneglycol: | 6% |
| ? | Triethylene diamine and stannous octoate: | 0.8% |
| ? | Water: | 0.2% |
| ? | The oleic acid diethylamine: | 0.08% |
| ? | 2, the 6-tertiary butyl-4-methylphenol: | 0.8% |
| The B material: | Diphenylmethanediisocyanate: | 50% |
Its preparation method is as follows:
At first, polycarbonate polyol and diphenylmethanediisocyanate are placed in the baking oven to descend to dry by the fire 8h at 70 ℃, standby;
Secondly, add 1 in the polycarbonate polyol after baking, the 4-butyleneglycol, triethylene diamine and stannous octoate, water, the oleic acid diethylamine, 2, the 6-tertiary butyl-4-methylphenol mixes and forms the A material;
At last, the B after A material and the baking is expected that isocyanic ester adds respectively in the A of casting molding machine, the B charging basket, be heated to 45 ℃ of casting, make through 3 minutes slakings at the bottom of the polyurethane shoe.
The performance of material for sole of shoe sees Table 1.
Embodiment 1
Its proportioning raw materials is as follows:
| The A material: | Polycarbonate polyol: | 40% |
| ? | 1, the 4-butyleneglycol: | 6% |
| ? | Triethylene diamine and stannous octoate: | 0.8% |
| ? | Water: | 0.2% |
| ? | The oleic acid diethylamine: | 0.08% |
| ? | 2, the 6-tertiary butyl-4-methylphenol: | 0.?8% |
| ? | Conductive titanium dioxide: | 3% |
| The B material: | Hexamethylene diisocyanate: | 47% |
Its preparation method is as follows:
(1) pre-treatment:
A, with the titanate coupling agent of the alcohol dilution 1g of 5ml, mix with the conductive titanium dioxide of 100g, mixed filler is put into vacuum drying oven, 70 ℃ of bakings 5 hours down.
B, with polycarbonate polyol, hexamethylene diisocyanate is placed in the baking oven at 70 ℃ of baking 8h down.
(2) add 1 in the polycarbonate polyol after baking, the 4-butyleneglycol, triethylene diamine and stannous octoate, water, the oleic acid diethylamine, 2, the 6-tertiary butyl-4-methylphenol coats the conductive titanium dioxide of handling, and mixes to form the A material;
(3) B that A material and hexamethylene diisocyanate baking back are formed expects to add respectively to be heated to 45 ℃ of casting among the A, B charging basket of casting molding machine, promptly get polyurethane shoe through 3 minutes slakings at the bottom of.The performance of material for sole of shoe sees Table 1.
Embodiment 2
Its proportioning raw materials is as follows:
| The A material: | Polycarbonate polyol: | 40% |
| ? | 1, the 4-butyleneglycol: | 6% |
| ? | Triethylene diamine and stannous octoate: | 0.8% |
| ? | Water: | 0.2% |
| ? | The oleic acid diethylamine: | 0.08% |
| ? | 2, the 6-tertiary butyl-4-methylphenol: | 0.?8% |
| ? | The conduction mica: | 3% |
| The B material: | Hexamethylene diisocyanate: | 47% |
Its preparation method is as follows:
(1) pre-treatment:
A, with the titanate coupling agent of the alcohol dilution 1g of 5ml, mix with the conduction mica of 100g, mixed filler is put into vacuum drying oven, 70 ℃ of bakings 5 hours down.
B, with polycarbonate polyol, hexamethylene diisocyanate is placed in the baking oven at 70 ℃ of baking 8h down.
(2) add 1 in the polycarbonate polyol after baking, the 4-butyleneglycol, triethylene diamine and stannous octoate, water, the oleic acid diethylamine, 2, the 6-tertiary butyl-4-methylphenol coats the conductive titanium dioxide of handling, and mixes to form the A material;
(3) B that A material and hexamethylene diisocyanate baking back are formed expects to add respectively to be heated to 45 ℃ of casting among the A, B charging basket of casting molding machine, promptly get polyurethane shoe through 3 minutes slakings at the bottom of.The performance of material for sole of shoe sees Table 1.
Embodiment 3
With the amount increase of conductive titanium dioxide is 5%, and other is the same with embodiment 1.The performance of material for sole of shoe sees Table 1.
Embodiment 4:
It is 5% that the micaceous amount of will conducting electricity increases, and other is the same with embodiment 2.The performance of material for sole of shoe sees Table 1.
Performance at the bottom of table 1 polyurethane shoe
| At the bottom of the polyurethane shoe | Volume resistance/Ω cm | Wear resistance/mm 3 |
| The comparative example | 1.2×10 10 | 247.5 |
| Embodiment 1 | 5.2×10 8 | 99.0 |
| Embodiment 2 | 6.6×10 8 | 185.3 |
| Embodiment 3 | 4.6×10 8 | 117.9 |
| Embodiment 4 | 3.7×10 8 | 136.7 |
The volume resistance of sole and wear resistance all are that the examination criteria according to GB GB21148-2007 records.As can be seen from Table 1, compare with the comparative example with the prepared polyurethane shoe material of 4 embodiment provided by the present invention and not only to have anlistatig performance, and wear resistance has also obtained significant raising.
Above specific embodiment only is several preferred embodiment provided by the present invention, and for material is carried out the performance comparison test, so it is stable that four kinds of embodiment components enumerating keep as far as possible, here need to prove, multiple chainextender, catalyzer, whipping agent, surfactant, oxidation inhibitor, static inhibitor and the mineral filler of the record of the present application content part can be carried out arbitrary combination with polyvalent alcohol and isocyanic ester, can make similar wear-resisting antistatic polyurethane material of performance and the footwear material of making thereof equally.
Claims (11)
1. wear-resisting antistatic polyurethane material, mixing cast by raw material A and raw material B forms, it is characterized in that, described raw material A comprises that mass percent is the polyvalent alcohol of 30%-45%, the chainextender of 3%-9%, the catalyzer of 0.5%-0.9%, the whipping agent of 0.05%-0.2%, the surfactant of 0.05%-0.1%, the oxidation inhibitor of 0.5%-1%, and the inorganic conductive powder of 1%-10%; Described B material is that mass percent is the isocyanic ester of 40%-55%.
2. wear-resisting antistatic polyurethane material according to claim 1 is characterized in that, described chainextender is ethylene glycol, glycerol and 1, one or more in the 4-butyleneglycol; Described whipping agent is a water; Described surfactant is: one or more in oleic acid diethylamine, stearic acid diethanolamine and the dodecyl benzene disulfonic acid; Described oxidation inhibitor is 2, the 6-tertiary butyl-4-methylphenol.
3. wear-resisting antistatic polyurethane material according to claim 1, it is characterized in that, described catalyzer is the mixture of organic amine and organic tin, and described organic amine is one or more in triethylene diamine, triethylamine, Tributylamine, dimethyl benzyl amine and the five methyl diethylentriamine; Described organic tin is one or more in stannous octoate, tin acetate, stannous octoate, dibutyl tin laurate and the tin laurate.
4. wear-resisting antistatic polyurethane material according to claim 1, described inorganic conductive powder are one or more in conductive titanate dioxide powder, conduction barium sulfate powder and the conductive mica powder.
5. wear-resisting antistatic polyurethane material according to claim 1 is characterized in that described inorganic conductive powder is coated with one deck hydrophobic nature coupling agent.
6. wear-resisting antistatic polyurethane material according to claim 5 is characterized in that: described coupling agent is one or more in titanic acid ester, phosphoric acid ester, boric acid ester or the aluminic acid ester.
7. the described wear-resisting antistatic polyurethane preparation methods of claim 1, it comprises the steps:
(1) polyvalent alcohol and isocyanic ester are placed in the baking oven respectively toast, standby;
(2) add chainextender, catalyzer, whipping agent, surfactant, oxidation inhibitor and inorganic conductive powder in the polyvalent alcohol after above-mentioned baking, and mix formation A material;
(3) with A material and B material isocyanic ester mixing casting, make wear-resisting antistatic polyurethane material.
8. wear-resisting antistatic polyurethane preparation methods according to claim 7 is characterized in that, described inorganic conductive powder adopts coupling agent to carry out the coating pre-treatment of following steps:
A, with coupling agent and thinner according to the ratio dissolving of 1:5, mix;
B, the inorganic conductive powder added in the above-mentioned solution mix;
C, mixed inorganic conductive powder is put into vacuum drying oven baking finish the coating pre-treatment.
9. wear-resisting antistatic polyurethane preparation methods according to claim 8 is characterized in that: the consumption of coupling agent is the 0.5-3% of inorganic conductive powder quality.
10. wear-resisting antistatic polyurethane preparation methods according to claim 8 is characterized in that: described thinner is ethanol, toluene or dimethylbenzene.
11. wear-resisting antistatic polyurethane preparation methods according to claim 8 is characterized in that: described coupling agent solution adopts ultrasonic wave to mix with the inorganic conductive powder.
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| CN102337020A (en) * | 2011-06-24 | 2012-02-01 | 苏州新纶超净技术有限公司 | Anti-static polyurethane elastomer material used under ultralow humidity condition and preparation method thereof |
| CN102432823A (en) * | 2011-08-25 | 2012-05-02 | 吴江市北厍盛源纺织品助剂厂 | Water-soluble antistatic polyurethane |
| CN102532469A (en) * | 2011-12-28 | 2012-07-04 | 南京双威生物医学科技有限公司 | Graphite composite modified fire-retardant anti-static polyurethane and adhesive plaster |
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| CN102337020A (en) * | 2011-06-24 | 2012-02-01 | 苏州新纶超净技术有限公司 | Anti-static polyurethane elastomer material used under ultralow humidity condition and preparation method thereof |
| CN102337020B (en) * | 2011-06-24 | 2013-03-20 | 苏州新纶超净技术有限公司 | Anti-static polyurethane elastomer material used under ultralow humidity condition and preparation method thereof |
| CN102432823A (en) * | 2011-08-25 | 2012-05-02 | 吴江市北厍盛源纺织品助剂厂 | Water-soluble antistatic polyurethane |
| CN102532469A (en) * | 2011-12-28 | 2012-07-04 | 南京双威生物医学科技有限公司 | Graphite composite modified fire-retardant anti-static polyurethane and adhesive plaster |
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| CN103289232A (en) * | 2013-05-31 | 2013-09-11 | 苏州市景荣科技有限公司 | Antistatic PVC (Poly Vinyl Chloride) sole foaming material |
| CN103570910A (en) * | 2013-10-15 | 2014-02-12 | 苏州市景荣科技有限公司 | Anionic polyurethane sole material |
| CN104262569A (en) * | 2014-09-04 | 2015-01-07 | 苏州市景荣科技有限公司 | High-wear-resistance polyurethane shoe material and manufacturing method thereof |
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| CN107523041A (en) * | 2017-06-30 | 2017-12-29 | 苏州奥斯汀新材料科技有限公司 | A kind of Antistatic type method for preparing thermoplastic polyurethane elastomer |
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| CN107663379A (en) * | 2017-10-24 | 2018-02-06 | 蚌埠隆华压铸机有限公司 | Die casting machine Special wear-resistant anti-static material |
| CN107778831A (en) * | 2017-11-01 | 2018-03-09 | 安徽鼎隆重工科技有限公司 | Die casting machine cooler high-abrasive material |
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| CN110894352A (en) * | 2019-11-08 | 2020-03-20 | 深圳市新纶科技股份有限公司 | Polyurethane material composition, polyurethane shoe material and preparation method thereof |
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| CN112029220A (en) * | 2020-08-18 | 2020-12-04 | 温州金鸿远鞋业有限公司 | Wear-resistant women's shoes and preparation method thereof |
| CN112940486A (en) * | 2021-01-26 | 2021-06-11 | 苏州天华超净科技股份有限公司 | Polyurethane material for anti-static shoe sole and anti-static shoe |
| CN113980221A (en) * | 2021-11-09 | 2022-01-28 | 苏州普诺兹电子有限公司 | Preparation method of antistatic polyurethane foam |
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Application publication date: 20110216 |