CN105330804A - Transparent wear-resisting polyurethane shoe material - Google Patents
Transparent wear-resisting polyurethane shoe material Download PDFInfo
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- CN105330804A CN105330804A CN201510778380.6A CN201510778380A CN105330804A CN 105330804 A CN105330804 A CN 105330804A CN 201510778380 A CN201510778380 A CN 201510778380A CN 105330804 A CN105330804 A CN 105330804A
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- shoe material
- titanium dioxide
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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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
-
- 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
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention discloses a transparent wear-resisting polyurethane shoe material. The material is composed of diisocyanate, polyester polyol, trimethylolpropane triacrylate, an organic tin catalyst, isophorone diamine, phenyl salicylate, trimethylolpropane, dimethicone, polyvinyl alcohol, dimethicone, dimethylolpropionic acid, transparent packing and water. According to the transparent wear-resisting polyurethane shoe material, the formula is adjusted, the specific polyester polyol is adopted for production of polyurethane, the organic packing with the refractive index close to that of the polyurethane is adopted, and the polyurethane shoe material with the excellent physical and mechanical performance, excellent processability and high transparency is obtained.
Description
Technical field
The present invention relates to a kind of polyurethane shoe material.More particularly, the present invention relates to a kind of transparent wear polyurethane shoe material.
Background technology
Urethane is a kind of high molecular synthetic material of excellent property, not only has the elasticity of rubber but also have the hardness of plastics, but also have good mechanical property, wear resistance and rebound performance, utilizes its these advantages to can be used to make the wheel of roller-skates.Current footwear material market is along with the continuous expansion of polyurethane field, and increasing to the demand of polyurethane shoe material, quality requirements is more and more higher.Current polyurethane shoe material produce producer requires that goods should good, the good toughness of outward appearance, and sanitation performance is good, proportion is little, and cost is low, also will keep basic transparency, glossiness.In the face of footwear material products is constantly brought forth new ideas upgrading, research and develop new polyurethane material, become the emphasis of research institutions and manufacturer's concern.
Summary of the invention
For the weak point existed in above-mentioned technology, the invention provides a kind of transparent wear polyurethane shoe material, by adjustment formula, by specific polyester polyol being used as the production of urethane, prepare the mineral filler close with urethane refractive index, prepare physical and mechanical property excellence, processing characteristics is excellent, the polyurethane shoe material that transparency is high.
The technical solution used in the present invention is:
A kind of transparent wear PU footwear material, comprises the component of following weight part:
Preferably, described isocyanic ester is 4, the 4 ' one in-diphenylmethanediisocyanate, tolylene diisocyanate or isophorone diisocyanate.
Preferably, described polyester polyol is adipic acid type polyester polyol, and described adipic acid type polyester polyol is by hexanodioic acid and 1,6-butyleneglycol and 1,4-cyclohexanedimethanol reacts and obtains, and wherein the molecular weight of this polyester polyol is 2000 ~ 5000g/mol.
Preferably, described transparent filler is the coated nanometer titanium dioxide of sial.
Preferably, the preparation method of described transparent filler is:
S1: be in the nanometer titanium dioxide suspension slurry of 6.5 ~ 7 at pH, under agitation add the mixed solution of liquid sodium aluminate and water glass, add-on is 15% of nanometer titanium dioxide weight with the total amount of water glass and sodium aluminate;
S2: under agitation pass into CO (carbon monoxide converter) gas and carry out carbonization hydrolysis, the temperature of hydrolysis reaction is 30 ~ 40 DEG C, hydrolysis time is 2 ~ 3 hours, and sodium aluminate and water glass are under the effect of carbon monoxide, and the surface that sial complex sol even compact is coated on nanometer titanium dioxide is separated out in hydrolysis;
S3: the filter cake that slurries filtration to the water content after coated is less than 40%, 90 ~ 110 DEG C of oven dry, obtains transparent filler.
Preferably, in described nanometer titanium dioxide suspension slurry, the particle diameter of nanometer titanium dioxide is 30 ~ 70nn, and in slurry, nanometer titanium dioxide percentage concentration is 15 ~ 20wt%.
Preferably, in described sodium aluminate and water glass mixed solution, the mol ratio of silicon, aluminium is 3:2 ~ 2:3.
The invention has the beneficial effects as follows:
(1) urethane by specific polyester polyol and di-isocyanate reaction are obtained, stable mechanical performance, wears away low;
(2) by adding the mineral filler close with urethane refractive index, the urethane physical and mechanical property prepared is excellent, and processing characteristics is excellent, and the footwear material adopting this polyurethane material to prepare has good transparency, glossiness and good toughness, and proportion is little.
Embodiment
Embodiments of the present invention are described in detail below with reference to specific embodiment.To the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure reaching technique effect can fully understand and implement according to this.
If do not specialize, the conventional means that the technique means adopted in embodiment is well known to those skilled in the art, the raw material adopted also be can business obtain.The various process do not described in detail and method are ordinary methods as known in the art.
Embodiment 1
Transparent wear PU footwear material, comprises the component of following weight part: 4,4 '-diphenylmethanediisocyanates 45 parts; Polyester polyol 40 parts; Viscoat 295 2 parts; Organotin catalysts 1 part; Isophorone diamine 1 part; Salicylic acid phenyl ester 0.8 part; TriMethylolPropane(TMP) 2.5 parts; Dimethyl silicone oil 2 parts; Polyvinyl alcohol 1 part; Benzoyl peroxide 0.8 part; Dimethylol propionic acid 0.5 part; Transparent filler 2 parts; Whitfield's ointment 2.5 parts.
Embodiment 2
Transparent wear PU footwear material, comprises the component of following weight part: 4,4 '-diphenylmethanediisocyanates 55 parts; Polyester polyol 50 parts; Viscoat 295 5 parts; Organotin catalysts 3 parts; Isophorone diamine 3 parts; Salicylic acid phenyl ester 1.5 parts; TriMethylolPropane(TMP) 6 parts; Dimethyl silicone oil 5 parts; Polyvinyl alcohol 4 parts; Benzoyl peroxide 2 parts; Dimethylol propionic acid 4.5 parts; Transparent filler 5 parts; Whitfield's ointment 3 parts.
Embodiment 3
Transparent wear PU footwear material, comprises the component of following weight part: 4,4 '-diphenylmethanediisocyanates 50 parts; Polyester polyol 45 parts; Viscoat 295 3 parts; Organotin catalysts 2 parts; Isophorone diamine 2 parts; Salicylic acid phenyl ester 1 part; TriMethylolPropane(TMP) 3 parts; Dimethyl silicone oil 4 parts; Polyvinyl alcohol 1 ~ 4 part; Benzoyl peroxide 1 part; Dimethylol propionic acid 2 parts; Transparent filler 4 parts; Whitfield's ointment 3 parts.
In above embodiment, polyester polyol is adipic acid type polyester polyol, and it is reacted by hexanodioic acid and 1,6-butyleneglycol and 1,4 cyclohexane dimethanol and obtained, and wherein the molecular weight of this polyester polyol is 2000 ~ 5000g/mol.
In above embodiment, the preparation method of transparent filler is:
S1: the particle diameter being 6.5 ~ 7 at pH is in 30 ~ 70nn nanometer titanium dioxide suspension slurry, in slurry, nanometer titanium dioxide percentage concentration is 15 ~ 20wt%, under agitation add the mixed solution of liquid sodium aluminate and water glass, add-on is 15% of nanometer titanium dioxide weight with the total amount of water glass and sodium aluminate, in sodium aluminate and water glass mixed solution, the mol ratio of silicon, aluminium is 3:2 ~ 2:3;
S2: under agitation pass into CO (carbon monoxide converter) gas and carry out carbonization hydrolysis, the temperature of hydrolysis reaction is 30 ~ 40 DEG C, hydrolysis time is 2 ~ 3 hours, and sodium aluminate and water glass are under the effect of carbon monoxide, and the surface that sial complex sol even compact is coated on nanometer titanium dioxide is separated out in hydrolysis;
S3: the filter cake that slurries filtration to the water content after coated is less than 40%, 90 ~ 110 DEG C of oven dry, obtains transparent filler.
Comparative example 1
Transparent wear PU footwear material, its component is identical with embodiment 1 with content, and difference is: adopt polyether glycol PPG to substitute polyester polyol.
Comparative example 2
Transparent wear PU footwear material, its component is identical with embodiment 1 with content, and difference is: polyester polyol adopts polycarbonate diol.
Comparative example 3
Transparent wear PU footwear material, its component is identical with embodiment 1 with content, and difference is: polyester polyol adopts adipic acid type polyester trivalent alcohol.
Comparative example 4
Transparent wear PU footwear material, its component is identical with embodiment 1 with content, and difference is: because nanometer titanium dioxide substitutes transparent filler.
The performance of the goods that embodiment and comparative example obtain is as following table
Claims (7)
1. a transparent wear polyurethane shoe material, is characterized in that, comprises the component of following weight part:
2. transparent wear polyurethane shoe material as claimed in claim 1, it is characterized in that, described isocyanic ester is 4, the 4 ' one in-diphenylmethanediisocyanate, tolylene diisocyanate or isophorone diisocyanate.
3. transparent wear polyurethane shoe material as claimed in claim 1, it is characterized in that, described polyester polyol is adipic acid type polyester polyol, described adipic acid type polyester polyol is by hexanodioic acid and 1,6-butyleneglycol and 1,4-cyclohexanedimethanol reacts and obtains, and wherein the molecular weight of this polyester polyol is 2000 ~ 5000g/mol.
4. transparent wear polyurethane shoe material as claimed in claim 1, is characterized in that, described transparent filler is the coated nanometer titanium dioxide of sial.
5. the transparent wear polyurethane shoe material as described in claim 1 or 4, is characterized in that, the preparation method of described transparent filler is:
S1: be in the nanometer titanium dioxide suspension slurry of 6.5 ~ 7 at pH, under agitation add the mixed solution of liquid sodium aluminate and water glass, add-on is 15% of nanometer titanium dioxide weight with the total amount of water glass and sodium aluminate;
S2: under agitation pass into CO (carbon monoxide converter) gas and carry out carbonization hydrolysis, the temperature of hydrolysis reaction is 30 ~ 40 DEG C, hydrolysis time is 2 ~ 3 hours, and sodium aluminate and water glass are under the effect of carbon monoxide, and the surface that sial complex sol even compact is coated on nanometer titanium dioxide is separated out in hydrolysis;
S3: the filter cake that slurries filtration to the water content after coated is less than 40%, 90 ~ 110 DEG C of oven dry, obtains transparent filler.
6. transparent wear polyurethane shoe material as claimed in claim 5, it is characterized in that, in described nanometer titanium dioxide suspension slurry, the particle diameter of nanometer titanium dioxide is 30 ~ 70nn, and in slurry, nanometer titanium dioxide percentage concentration is 15 ~ 20wt%.
7. transparent wear polyurethane shoe material as claimed in claim 5, is characterized in that, in described sodium aluminate and water glass mixed solution, the mol ratio of silicon, aluminium is 3:2 ~ 2:3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510778380.6A CN105330804A (en) | 2015-11-13 | 2015-11-13 | Transparent wear-resisting polyurethane shoe material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510778380.6A CN105330804A (en) | 2015-11-13 | 2015-11-13 | Transparent wear-resisting polyurethane shoe material |
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| CN105330804A true CN105330804A (en) | 2016-02-17 |
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| CN201510778380.6A Pending CN105330804A (en) | 2015-11-13 | 2015-11-13 | Transparent wear-resisting polyurethane shoe material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085174A (en) * | 2016-06-12 | 2016-11-09 | 雄子（上海）新材料科技有限公司 | polyurethane coating and preparation method thereof |
| CN109666285A (en) * | 2018-11-30 | 2019-04-23 | 长春安旨科技有限公司 | A kind of wear-resisting high-molecular composite material |
| CN112724657A (en) * | 2020-12-29 | 2021-04-30 | 永佳工业车辆(苏州)有限公司 | Structurally optimized compression-resistant wear-resistant polyurethane caster and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850927A (en) * | 2006-05-18 | 2006-10-25 | 复旦大学 | Water-soluble nano composite polyester-polyurethane coating material, and its preparing method |
| CN102417588A (en) * | 2011-11-18 | 2012-04-18 | 温州大学 | Polyester polyurethane sole stoste and preparation method thereof |
| CN102786792A (en) * | 2012-08-07 | 2012-11-21 | 深圳市新纶科技股份有限公司 | Anti-yellowing polyurethane shoe material and preparation method thereof |
| CN103289046A (en) * | 2013-05-31 | 2013-09-11 | 苏州市景荣科技有限公司 | Wear-resistant polyurethane sole material |
| WO2015150237A1 (en) * | 2014-03-31 | 2015-10-08 | Bayer MAterialScience (China) Company Ltd. | Transparent and abrasion resistant polyurethane elastomer and process for preparing same |
-
2015
- 2015-11-13 CN CN201510778380.6A patent/CN105330804A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850927A (en) * | 2006-05-18 | 2006-10-25 | 复旦大学 | Water-soluble nano composite polyester-polyurethane coating material, and its preparing method |
| CN102417588A (en) * | 2011-11-18 | 2012-04-18 | 温州大学 | Polyester polyurethane sole stoste and preparation method thereof |
| CN102786792A (en) * | 2012-08-07 | 2012-11-21 | 深圳市新纶科技股份有限公司 | Anti-yellowing polyurethane shoe material and preparation method thereof |
| CN103289046A (en) * | 2013-05-31 | 2013-09-11 | 苏州市景荣科技有限公司 | Wear-resistant polyurethane sole material |
| WO2015150237A1 (en) * | 2014-03-31 | 2015-10-08 | Bayer MAterialScience (China) Company Ltd. | Transparent and abrasion resistant polyurethane elastomer and process for preparing same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085174A (en) * | 2016-06-12 | 2016-11-09 | 雄子（上海）新材料科技有限公司 | polyurethane coating and preparation method thereof |
| CN109666285A (en) * | 2018-11-30 | 2019-04-23 | 长春安旨科技有限公司 | A kind of wear-resisting high-molecular composite material |
| CN112724657A (en) * | 2020-12-29 | 2021-04-30 | 永佳工业车辆(苏州)有限公司 | Structurally optimized compression-resistant wear-resistant polyurethane caster and preparation method thereof |
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Application publication date: 20160217 |