CN104972582A - Organic silicon release agent for polyurethane shoe soles - Google Patents
Organic silicon release agent for polyurethane shoe soles Download PDFInfo
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- CN104972582A CN104972582A CN201510435666.4A CN201510435666A CN104972582A CN 104972582 A CN104972582 A CN 104972582A CN 201510435666 A CN201510435666 A CN 201510435666A CN 104972582 A CN104972582 A CN 104972582A
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Abstract
The invention relates to an organic silicon release agent for polyurethane shoe soles. According to the organic silicon release agent, alkyl modified silicone oil, low-molecular polyethylene and wax serve as raw materials; a non-ionic surface active agent and terminated polyether modified silicone oil serve as emulsifying agents; water serves as a dispersion medium; a high-shear emulsifying machine is used for conducting emulsification, and then the organic silicon release agent for the polyurethane shoe soles is obtained. The organic silicon release agent has the characteristics that the organic silicon release agent is waters-soluble, environmentally friendly, free of odor and solvent evaporation, good in demolding effect and shaping, free of scale after being used for demolding for many times, glossy and flawless, and the shoe soles can be stripped easily; meanwhile, the organic silicon release agent is low in manufacturing cost and excellent in demolding effect.
Description
Technical field
The invention belongs to technical field of mold release, relate to a kind of polyurethane shoe-sole silicone release.
Background technology
China is shoemaking exported country maximum in the world, it is reported, within 2012, reaches 10,000,000,000 pairs, and be worth 443.6 hundred million dollars, the first half of the year in 2015, footwear exported 51.1 hundred million pairs, were worth 17,900,000,000 dollars.In the footwear total amount of outlet, considerable part is had to be sport footwear.The feature of sport footwear is high resilience, and the large portion of sole is that polyurethane elastomeric materials is made.It obtains through injection mo(u)lding with urethane raw, in order to be convenient in demoulding, all in the mould of injection moulding, sprays the releasing agent such as silicone oil, wax class in advance, then injects urethane raw and adds thermal response again, the shaping rear demoulding.To the requirement of releasing agent, one is aqueous, environmental protective, the solvent-free volatilization of odorlessness; Two is that stripping result is good, without incrustation after the repeated multiple times demoulding; Three be the sole demoulding easily, forming, glossy, indefectible.Such releasing agent, for many years all by watt gram (Chem ~ Trend) company monopolizing of Germany, formula technique is more secret.
Through consulting China's patent, the patent for polyurethane shoe-sole is few.My company scientific research personnel is through looking through a great amount of information, through up to a hundred lab scales and tens pilot scales, with alkyl modified silicon oil, low molecular polyethylene and wax class for primary raw material, with nonionic and end capped polyether modified silicon oil non-ionic surface active agent for emulsifying agent, take water as decentralized medium, through high-shear emulsion machine and duct type mulser, be emulsified into stable emulsion oil-in-water, try out, after being watered 20 ~ 30 times, for the polyurethane shoe-sole demoulding through factory, stripping result is excellent, the continuous demoulding is after one week, then mold cleaning tool, up to a hundred times of release times.
Summary of the invention
For overcoming above-mentioned technical disadvantages, the invention provides
a kind ofpolyurethane shoe-sole silicone release, it has, and aqueous, environmental protective, the solvent-free volatilization of odorlessness, stripping result are good, forming, the feature such as glossy, indefectible.
The present invention solves the technical method that its technical problem adopts:
a kind ofpolyurethane shoe-sole silicone release, it with alkyl modified silicon oil, low molecular polyethylene and wax for raw material, with non-ionic surface active agent and end capped polyether modified silicon oil for emulsifying agent, take water as decentralized medium, and by high-shear emulsion machine emulsification, obtained corresponding polyurethane shoe-sole silicone release emulsifying agent.
Described alkyl modified silicon oil is first-selected silicone oil raw material, and be secondly methyl-silicone oil, hydroxy silicon oil and the alkyl-silicone oil comprising long chain alkyl modified silicon oil and middle long chain alkyl modified silicon oil, the length of alkyl chain is 4 ~ 18 carbon, and the alkyl of 8 ~ 12 carbon is first-selected.The consumption of alkyl-silicone oil is 10 ~ 80% of effective releasing agent, is preferably 30 ~ 60%.
Described low molecular polyethylene is melting point low (lower than 150 DEG C) Tissuemat E, and the consumption of low molecular polyethylene in releasing agent is 10 ~ 50%, is preferably 20 ~ 30%.
Described wax is mineral wax or vegetable wax, and wherein mineral wax can be paraffin, ceresine, and vegetable wax comprises insect wax or Brazil wax, and mineral wax fusing point is between 50 ~ 90 DEG C.
Described non-ionic surface active agent comprises polyoxyethylene carboxylate and alkyl alcohol ethoxylates, and their HLB value controls between 12 ~ 16, and cloud point controls between 50 ~ 100 DEG C, and consumption controls between 5 ~ 20% of wax total amount.
Described end capped polyether modified silicon oil non-ionic surface active agent is that methoxyl group or alkoxy end-capped allyl polyethenoxy ether and containing hydrogen silicone oil synthesize under platinum catalysis effect, for commercial products, viscosity between 100 ~ 300cs, consumption be alkyl modified silicon oil amount used 10 ~ 30% between.
When high-shear emulsion machine emulsification, heating-up temperature must higher than mixture fusing point more than 10 DEG C.
The average grain diameter of described polyurethane shoe-sole silicone release emulsifying agent controls within 1 μm, and solid content controls between 10 ~ 25%, and viscosity controls within 50cs.
The invention has the beneficial effects as follows: the quality of emulsion-type releasing agent, except raw materials used, particularly there are much relations with the granular size of emulsion and distributing homogeneity, if the particle of emulsion is thick, skewness, just easy breakdown of emulsion, even if not breakdown of emulsion, also the easy narrow area at mould tires out, and affects the demoulding and access times.And the kind of emulsion intercalation method and particle size and emulsifying agent and consumption have much relations.Want the good a certain oily substance of emulsification, first emulsifier hlb value is similar to the HLB value of emulsified oily wax or slightly height is a bit.For the emulsification of wax class, also to consider the cloud point of emulsifying agent, because wax class is solid, some melting points are up to more than 100 degree, the cloud point of emulsifying agent must higher than the melting point of wax, the emulsification of wax must be carried out under higher than the liquid state of its melting point, if the cloud point of emulsifying agent is lower than the melting point of wax, just can not play emulsification.The siliceous oily substance of this emulsion-type releasing agent, employing polyether modified silicon oil class non-ionic surface active agent is the key innovations of this technology, because structure is similar, polyether modified silicon oil class emulsifying agent and silicone oil part mix, silicone oil material can be emulsified into particle thin, even particle distribution, give stable O/w emulsion, the general hydroxyl of polyether modified silicon oil, isocyanate reaction easily and in urethane raw, and affecting stripping result. this releasing agent has aqueous, environmental protective, the solvent-free volatilization of odorlessness, stripping result is good, without incrustation after the repeated multiple times demoulding, the sole demoulding is easy, forming, glossy, the feature such as indefectible, simultaneously cheap, stripping result is excellent.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described.
a kind ofpolyurethane shoe-sole silicone release, it with alkyl modified silicon oil, low molecular polyethylene and wax for raw material, with non-ionic surface active agent and end capped polyether modified silicon oil for emulsifying agent, take water as decentralized medium, and by high-shear emulsion machine emulsification, obtained corresponding polyurethane shoe-sole silicone release emulsifying agent.
Described alkyl modified silicon oil is first-selected silicone oil raw material, and be secondly methyl-silicone oil, hydroxy silicon oil and the alkyl-silicone oil comprising long chain alkyl modified silicon oil and middle long chain alkyl modified silicon oil, the length of alkyl chain is 4 ~ 18 carbon, and the alkyl of 8 ~ 12 carbon is first-selected.The consumption of alkyl-silicone oil is 10 ~ 80% of effective releasing agent, is preferably 30 ~ 60%.
Described low molecular polyethylene is melting point low (lower than 150 DEG C) Tissuemat E, and the consumption of low molecular polyethylene in releasing agent is 10 ~ 50%, is preferably 20 ~ 30%.
Described wax is mineral wax or vegetable wax, and wherein mineral wax can be paraffin, ceresine, and vegetable wax comprises insect wax or Brazil wax, and mineral wax fusing point is between 50 ~ 90 DEG C.
Described non-ionic surface active agent comprises polyoxyethylene carboxylate and alkyl alcohol ethoxylates, and their HLB value controls between 12 ~ 16, and cloud point controls between 50 ~ 100 DEG C, and consumption controls between 5 ~ 20% of wax total amount.
Described end capped polyether modified silicon oil non-ionic surface active agent is that methoxyl group or alkoxy end-capped allyl polyethenoxy ether and containing hydrogen silicone oil synthesize under platinum catalysis effect, for commercial products, viscosity between 100 ~ 300cs, consumption be alkyl modified silicon oil amount used 10 ~ 30% between.
When high-shear emulsion machine emulsification, heating-up temperature must higher than mixture fusing point more than 10 DEG C.
The average grain diameter of described polyurethane shoe-sole silicone release emulsifying agent controls within 1 μm, and solid content controls between 10 ~ 25%, and viscosity controls within 50cs.
Embodiment 1: alkyl modified silicon oil 60 parts, low molecular polyethylene 20 parts, 20 parts, paraffin, this ~ 60 4 parts, dish, tween ~ 60 6 part, end capped polyether modified silicon oil 10 parts, propane diols 20 parts, adds reactor, after being heated to 80 DEG C of fusings, slowly add 80 DEG C of hot water, start high-speed stirred mulser, emulsification 60 minutes, then below cooling water temperature to 40 DEG C, filter discharging, obtain the emulsion-type releasing agent R1 of milky 20%.
Embodiment 2: alkyl modified silicon oil 40 parts, low molecular polyethylene 30 parts, 30 parts, paraffin, this ~ 60 5 parts, dish, tween ~ 60 5 part, end capped polyether modified silicon oil 10 parts, add jacketed electrical heating emulsifier, be heated to 80 DEG C of fusings, then under high-shear emulsion machine effect, slowly add hot water and the propane diols 20 parts of 90 DEG C, emulsification obtains the releasing agent emulsion R2 of 20%.
Embodiment 3: alkyl modified silicon oil 50 parts, 50 parts, paraffin, this ~ 60 5 parts, dish, tween ~ 60 5 part, methyl blocking polyether modified silicon oil 10 parts, add the emulsifier of chuck electric heating, be heated to after 85 DEG C of fusings stir evenly, under high shear forces, slowly add the hot water 200 parts of 90 DEG C, then add cold water and be cooled to less than 40 DEG C, filter the emulsion-type releasing agent R3 that discharging obtains 20%.
Embodiment 4: alkyl modified silicon oil 60 parts, low molecular polyethylene 40 parts, this ~ 20 4 parts, dish, tween ~ 60 6 part, end capped polyether modified silicon oil 10 parts, adds chuck electrical heating emulsifier together, be heated to 100 DEG C, fusing, adds the boiling water 200 parts of 100 DEG C several times under high speed shear, after add cold water and directly cool the oil-in-water releasing agent emulsion R4 obtaining 20%.
Embodiment 5: alkyl modified silicon oil 70 parts, vegetable wax 30 parts, alkyl alcohol ethoxylates P40 6 parts, isomeric alcohol polyethenoxy ether 1,310 4 parts, end capped polyether modified silicon oil 10 parts adds the emulsifier of chuck heating, is heated to 85 DEG C of fusings, slowly adds 85 DEG C of hot water and propane diols 20 parts under high velocity agitation, after add cold water and directly cool, obtain the oil-in-water releasing agent of 20%.Filtration obtains releasing agent 20% emulsion R5.
The performance of above-mentioned each emulsion is as follows:
| Numbering | Average grain diameter (μm) | The dewatering ability (3000r/min × 10min) of emulsion | 50 DEG C of 15 days stability | Freeze-thaw stability |
| R1 | 0.6 | Not stratified | Not stratified | Not stratified |
| R2 | 0.8 | Not stratified | Not stratified | Not stratified |
| R3 | 1 | Not stratified | Not stratified | Not stratified |
| R4 | 3.5 | Not stratified | Layering | Layering |
| R5 | 0.9 | Not stratified | Not stratified | Not stratified |
As can be seen from the above table, heat endurance and the low-temperature stability of the releasing agent emulsion of independent alkyl-silicone oil and low molecular polyethylene are poor, illustrate that intersolubility is not so good, and adopt the stability of emulsion of silicone oil emulsification together with paraffin or three better.
Embodiment 6: replace alkyl-silicone oil with methyl-silicone oil, all the other are all with embodiment 1.Found that, emulsion intercalation method is no problem, but emulsion is made into being watered multiple and will reducing by half of releasing agent working solution, just can reach the stripping result of example 1.
Embodiment 7: with embodiment 1, just emulsifying agent all coils TWEEN Series with this, and consumption adds and is twice, but without polyether modified silicon oil emulsifying agent, the centrifugal layering of result emulsion, illustrates that polyether modified silicon oil is indispensable.
Embodiment 8: with embodiment 1, just polyether modified silicon oil emulsifying agent used adopts hydroxyl terminated polyether modified silicon oil to make emulsifying agent, found that emulsion intercalation method is no problem, but the demoulding is difficult, reason is, do not have the isocyanate group generation cross-linking reaction in the hydroxyl of end-blocking and urethane raw, make demoulding difficulty.
Above-described embodiment Component Source:
Alkyl modified silicon oil: from synthesis.With laurylene and containing hydrogen silicone oil, addition under platinum catalyst effect is synthesized.Viscosity is about 200cs, low molecular polyethylene outsourcing, fusing point 105 DEG C; Paraffin, fusing point 56 ~ 60 DEG C, outsourcing; This dish, tween, outsourcing; End capped polyether, outsourcing, by Hangzhou, Di Weilai trade Co., Ltd provides, viscosity about 200cs; Non-end capped polyether modified silicon oil, from synthesis.Emulsion particle diameter is analyzed and is tested Co., Ltd's mensuration by the new powder of Chengdu essence.
Claims (8)
1.
a kind ofpolyurethane shoe-sole silicone release, it is characterized in that: it with alkyl modified silicon oil, low molecular polyethylene and wax for raw material, with non-ionic surface active agent and end capped polyether modified silicon oil for emulsifying agent, take water as decentralized medium, and by high-shear emulsion machine emulsification, obtained corresponding polyurethane shoe-sole silicone release emulsifying agent.
2. polyurethane shoe-sole silicone release as claimed in claim 1, it is characterized in that: described alkyl modified silicon oil is first-selected silicone oil raw material, secondly be methyl-silicone oil, hydroxy silicon oil and the alkyl-silicone oil comprising long chain alkyl modified silicon oil and middle long chain alkyl modified silicon oil, the length of alkyl chain is 4 ~ 18 carbon, and the alkyl of 8 ~ 12 carbon is first-selected, the consumption of alkyl-silicone oil is 10 ~ 80% of effective releasing agent, is preferably 30 ~ 60%.
3. polyurethane shoe-sole silicone release as claimed in claim 1, is characterized in that: described low molecular polyethylene is melting point low (lower than 150 DEG C) Tissuemat E, and the consumption of low molecular polyethylene in releasing agent is 10 ~ 50%, is preferably 20 ~ 30%.
4. polyurethane shoe-sole silicone release as claimed in claim 1, it is characterized in that: described wax is mineral wax or vegetable wax, wherein mineral wax can be paraffin, ceresine, and vegetable wax comprises insect wax or Brazil wax, and mineral wax fusing point is between 50 ~ 90 DEG C.
5. polyurethane shoe-sole silicone release as claimed in claim 1, it is characterized in that: described non-ionic surface active agent comprises polyoxyethylene carboxylate and alkyl alcohol ethoxylates, their HLB value controls between 12 ~ 16, cloud point controls between 50 ~ 100 DEG C, and consumption controls between 5 ~ 20% of wax total amount.
6. polyurethane shoe-sole silicone release as claimed in claim 1, it is characterized in that: described end capped polyether modified silicon oil non-ionic surface active agent is that methoxyl group or alkoxy end-capped allyl polyethenoxy ether and containing hydrogen silicone oil synthesize under platinum catalysis effect, for commercial products, viscosity between 100 ~ 300cs, consumption be alkyl modified silicon oil amount used 10 ~ 30% between.
7. polyurethane shoe-sole silicone release as claimed in claim 1, is characterized in that: when high-shear emulsion machine emulsification, heating-up temperature must higher than mixture fusing point more than 10 DEG C.
8. polyurethane shoe-sole silicone release as claimed in claim 1, is characterized in that: the average grain diameter of described polyurethane shoe-sole silicone release emulsifying agent controls within 1 μm, and solid content controls between 10 ~ 25%, and viscosity controls within 50cs.
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| CN201510435666.4A CN104972582A (en) | 2015-07-23 | 2015-07-23 | Organic silicon release agent for polyurethane shoe soles |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105252678A (en) * | 2015-11-06 | 2016-01-20 | 沈阳化工大学 | High-temperature-resistant wax-system environment-friendly polyurethane release agents and preparation method thereof |
| CN105969492A (en) * | 2016-05-06 | 2016-09-28 | 东莞市凯文化工有限公司 | Release agent special for rolling mill and preparation method thereof |
| CN106117925A (en) * | 2016-06-30 | 2016-11-16 | 嘉兴市哈妮鞋业有限公司 | Preparation rubber soles releasing agent |
| CN106182515A (en) * | 2016-06-30 | 2016-12-07 | 嘉兴市哈妮鞋业有限公司 | The preparation method of rubber soles releasing agent |
| CN106553297A (en) * | 2016-10-20 | 2017-04-05 | 沈阳化工大学 | A kind of palm wax and silicones Compositional type high-rebound polyurethane foaming product releasing agent |
| CN106626168A (en) * | 2016-08-23 | 2017-05-10 | 广东工业大学 | Aqueous emulsion organosilicon mold lubricant and preparation method and application thereof |
| CN108819052A (en) * | 2018-05-04 | 2018-11-16 | 苏州捷德瑞精密机械有限公司 | A kind of resin matrix system release agent and preparation method thereof |
| CN109434010A (en) * | 2018-12-14 | 2019-03-08 | 上海樱花化研化工科技有限公司 | A kind of aluminum alloy mould release agent composition and preparation method thereof |
| CN116694387A (en) * | 2023-05-16 | 2023-09-05 | 温州大学新材料与产业技术研究院 | Emulsifier for release agent and release agent prepared from emulsifier |
| CN118146557A (en) * | 2024-05-09 | 2024-06-07 | 杭州崇耀科技发展有限公司 | PU leather wet DMF rapid replacement cell regulator and preparation and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105252678A (en) * | 2015-11-06 | 2016-01-20 | 沈阳化工大学 | High-temperature-resistant wax-system environment-friendly polyurethane release agents and preparation method thereof |
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| CN105969492A (en) * | 2016-05-06 | 2016-09-28 | 东莞市凯文化工有限公司 | Release agent special for rolling mill and preparation method thereof |
| CN106117925A (en) * | 2016-06-30 | 2016-11-16 | 嘉兴市哈妮鞋业有限公司 | Preparation rubber soles releasing agent |
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| CN106553297A (en) * | 2016-10-20 | 2017-04-05 | 沈阳化工大学 | A kind of palm wax and silicones Compositional type high-rebound polyurethane foaming product releasing agent |
| CN108819052A (en) * | 2018-05-04 | 2018-11-16 | 苏州捷德瑞精密机械有限公司 | A kind of resin matrix system release agent and preparation method thereof |
| CN109434010A (en) * | 2018-12-14 | 2019-03-08 | 上海樱花化研化工科技有限公司 | A kind of aluminum alloy mould release agent composition and preparation method thereof |
| CN116694387A (en) * | 2023-05-16 | 2023-09-05 | 温州大学新材料与产业技术研究院 | Emulsifier for release agent and release agent prepared from emulsifier |
| CN116694387B (en) * | 2023-05-16 | 2024-09-24 | 温州大学新材料与产业技术研究院 | Emulsifier for release agent and release agent prepared from emulsifier |
| CN118146557A (en) * | 2024-05-09 | 2024-06-07 | 杭州崇耀科技发展有限公司 | PU leather wet DMF rapid replacement cell regulator and preparation and application thereof |
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Application publication date: 20151014 |