CN103275305A - Hyperbranched polyester polyol for polyurethane shoe sole and preparation method of hyperbranched polyester polyol - Google Patents
Hyperbranched polyester polyol for polyurethane shoe sole and preparation method of hyperbranched polyester polyol Download PDFInfo
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- CN103275305A CN103275305A CN201310184982XA CN201310184982A CN103275305A CN 103275305 A CN103275305 A CN 103275305A CN 201310184982X A CN201310184982X A CN 201310184982XA CN 201310184982 A CN201310184982 A CN 201310184982A CN 103275305 A CN103275305 A CN 103275305A
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Abstract
The invention relates to a hyperbranched polyester polyol for a polyurethane shoe sole and a preparation method of the hyperbranched polyester polyol and belongs to the technical field of high polymer materials. The hyperbranched polyester polyol has the characteristics of highly branching, three-dimensional network structure, multiple branched chains and the like, and is difficult to intertwine between molecules. The preparation method of the hyperbranched polyester polyol comprises the following steps of: preparing a polymer with a hyperbranched structure by taking trimethylolpropane and organic polyatomic acids as raw materials, and then adding organic polyhydric alcohols so as to react with the polymer with the hyperbranched structure for preparing the hyperbranched polyester polyol. The preparation method is simple, low in production cost and suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of polyester polyol and preparation method thereof, particularly a kind of for hyperbranched poly ester polyol at the bottom of the polyurethane shoe and preparation method thereof, belong to technical field of polymer materials.
Background technology
Microvoid polyurethane (PU) elastomerics has characteristics such as light weight, wear-resisting, folding, oil resistant, chemicals-resistant, and soft based on the polyurethane shoe material of microcellular polyurethane elastomer, comfortable and easy to wear, warming, high resilience are anti-skidding, and machine-shaping is simple.The polyurethane shoe material is to develop a kind of footwear synthetic resins faster, is widely used in producing playshoes, sports shoes, footware and sandals etc.It is that other footwear material lacks that the polyurethane shoe material has some unique character.
The polyurethane shoe material is based on sole.Polyurethane sole materials starts from the European industrialization of phase late 1960s, enters American market the seventies, and the eighties is very fast in global evolution, and its consumption is being stablized increase always.Pursuing low-cost, high quality, is the developing direction of polyurethane shoe bed material.Keeping reducing the density of moulded parts under the well behaved situation of urethane, slip resistance is provided, this is the main demand in market at the bottom of the polyurethane shoe.
Reducing density is one of common requirement of polyurethane shoe material supplier, can reduce cost like this, with traditional non-polyurethane shoe material competition such as low density EVA and some PVC.Low-density polyurethane footwear material should satisfy these points:
Dimensional stabilizing, namely the footwear material does not shrink, and is non-warping;
Be easy to processing, namely mixing of materials, compound better than the latitude property that flows is good, and the goods demould time is short, surface quality good, and is good with the cohesiveness of other independent components of footwear such as embedded thing, upper of a shoe, outer bottom;
Performance is satisfactory.This is a very complicated problem in actual Application and Development.
Hyperbranched polymer is the globular macromolecule that a class has highly branched structure, on primary structure, hyperbranched polymer is the macromole with " nuclear-shell " structure, have numerous functional groups on " shell " of molecule, solvability in organic solvent is big, compares with linear molecule, and the viscosity of its molten mass and solution is lower, its second-order transition temperature is subjected to the influence of " stratum nucleare " structure less, is subjected to the influence of " shell " functional group bigger.Hyperbranched polymer makes it have many special nature because of its special structure.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of hyperbranched poly ester polyol is provided, and is used for changing structure at molecular level at the bottom of the polyurethane shoe, thereby generates at the bottom of the polyurethane shoe of low density, high strength, high tenacity.
For solving above technical problem, the invention provides a kind of hyperbranched poly ester polyol, its structural formula is:
Wherein, R is (CH
2)
a, 1≤a≤10; R
1Be (CH
2)
b, 1≤b≤10; A, b is natural number.
The present invention also provides the preparation method of above-mentioned hyperbranched poly ester polyol, and described preparation method comprises the steps:
(1) preparation of dissaving structure polymkeric substance
Percentage composition meter by weight, TriMethylolPropane(TMP) with 10% ~ 25%, the acid of 45% ~ 65% organic multicomponent add in the reactor, begin heating, treat to begin to stir after the above-mentioned reactants dissolved, when described reactor temperature rises to 170 ℃ ~ 200 ℃, feed nitrogen protection, when described reactor temperature rises to 220 ℃ ~ 250 ℃, the catalyzer of adding 0.001% ~ 0.003% is in described reactor and keep this temperature range reaction 3h ~ 7h, makes the dissaving structure polymkeric substance;
(2) preparation of hyperbranched poly ester polyol
Percentage composition meter by weight, after step (1) reaction is finished, organic polyhydric alcohol with 15% ~ 30% adds in the aforesaid reaction vessel, when described reactor temperature rises to 120 ℃ ~ 170 ℃, keep this temperature range reaction 5h ~ 10h and simultaneously described reactor is vacuumized the water that generates with except dereaction, then described reactor temperature is risen to 200 ℃ ~ 250 ℃ and keep this temperature range reaction 10h ~ 24h, make the hyperbranched poly ester polyol;
More than the percentage composition of each component with the weight of component in component in the step (1) and the step (2) be 100% to calculate.
Wherein, in the step (1), described organic multicomponent acid is the polyprotonic acid of two functionality, a kind of in the diacid of selecting oneself, terephthalic acid, the phthalic acid; Described catalyzer is a kind of in the vitriol oil, tosic acid, tetrabutyl titanate, titanium isopropylate, the sulfur oxychloride.
In the step (2), described organic polyhydric alcohol is the polyvalent alcohol of two functionality, is selected from a kind of in ethylene glycol, Diethylene Glycol, propylene glycol, neopentyl glycol, the methyl propanediol.
Hyperbranched poly ester polyol of the present invention can be used at the bottom of the polyurethane shoe.
Because the enforcement of technique scheme, the present invention compared with prior art has following advantage:
Characteristics such as that the hyperbranched poly ester polyol of the present invention preparation has is highly branched, tridimensional network is arranged, intermolecular difficult winding, side chain are many.
The hyperbranched poly ester polyol of the present invention's preparation is used for having reduced the density of sole at the bottom of the polyurethane shoe, has improved intensity, has increased folding number.
Preparation method of the present invention is simple, and production cost is lower, is applicable to large-scale industrial production.
Embodiment
The raw material that adopts among the following embodiment is commercially available standard industry product.
The preparation method's of a kind of hyperbranched poly ester polyol of the present invention step and synthetic route are as follows:
Wherein, R is (CH
2)
a, 1≤a≤10; R
1Be (CH
2)
b, 1≤b≤10; A, b is natural number.
(1) preparation of dissaving structure polymkeric substance
Percentage composition meter by weight, TriMethylolPropane(TMP) with 10% ~ 25%, the acid of 45% ~ 65% organic multicomponent add in the reactor, begin heating, treat to begin to stir after the above-mentioned reactants dissolved, when described reactor temperature rises to 170 ℃ ~ 200 ℃, feed nitrogen protection, when described reactor temperature rises to 220 ℃ ~ 250 ℃, the catalyzer of adding 0.001% ~ 0.003% is in described reactor and keep this temperature range reaction 3h ~ 7h, makes the dissaving structure polymkeric substance;
(2) preparation of hyperbranched poly ester polyol
Percentage composition meter by weight, after step (1) reaction is finished, organic polyhydric alcohol with 15% ~ 30% adds in the aforesaid reaction vessel, when described reactor temperature rises to 120 ℃ ~ 170 ℃, keep this temperature range reaction 5h ~ 10h and simultaneously described reactor is vacuumized the water that generates with except dereaction, then described reactor temperature is risen to 200 ℃ ~ 250 ℃ and keep this temperature range reaction 10h ~ 24h, make the hyperbranched poly ester polyol;
More than the percentage composition of each component with the weight of component in component in the step (1) and the step (2) be 100% to calculate.
Embodiment 1
(1) selection has the reactor of agitator and nitrogen inlet, 134.17g TriMethylolPropane(TMP), 438.42g hexanodioic acid are added in the reactor, begin heating, treat to begin to stir after the above-mentioned reactants dissolved, when reactor temperature rises to 170 ℃, feed nitrogen protection, when reactor temperature rises to 220 ℃, adding 0.015g tetrabutyl titanate is in reactor and keep this thermotonus 4h, makes the dissaving structure polymkeric substance;
(2) after step (1) reaction is finished, 186.20g ethylene glycol is added in the aforesaid reaction vessel, when reactor temperature rises to 150 ℃, keep this thermotonus 10h and simultaneously described reactor is vacuumized the water that generates with except dereaction, then described reactor temperature is risen to 220 ℃ and keep this thermotonus 12h, make the hyperbranched poly ester polyol;
Product polyester polyol after reaction finishes to step (2) is tested, and test result is as follows: acid number is 0.23mgKOH/g, and hydroxyl value is 86mgKOH/g, and moisture is 0.01526%, and chromatic number is 20 ~ 30APHA.
Embodiment 2
(1) selection has the reactor of agitator and nitrogen inlet, 268.34g TriMethylolPropane(TMP), 584.43g terephthalic acid are added in the reactor, begin heating, treat to begin to stir after the above-mentioned reactants dissolved, when reactor temperature rises to 180 ℃, feed nitrogen protection, when reactor temperature rises to 230 ℃, the adding 0.022g vitriol oil is in reactor and keep this temperature range reaction 5h, makes the dissaving structure polymkeric substance;
(2) after step (1) reaction is finished, 248.27g ethylene glycol is added in the aforesaid reaction vessel, when reactor temperature rises to 160 ℃, keep this thermotonus 10h and simultaneously described reactor is vacuumized the water that generates with except dereaction, then described reactor temperature is risen to 250 ℃ and keep this thermotonus 10h, make the hyperbranched poly ester polyol;
Product polyester polyol after reaction finishes to step (2) is tested, and test result is as follows: acid number is 0.31mgKOH/g, and hydroxyl value is 88mgKOH/g, and moisture is 0.01631%, and chromatic number is 20 ~ 30APHA.
Embodiment 3
(1) selection has the reactor of agitator and nitrogen inlet, 134.17g TriMethylolPropane(TMP), 511.49g hexanodioic acid are added in the reactor, begin heating, treat to begin to stir after the above-mentioned reactants dissolved, when reactor temperature rises to 180 ℃, feed nitrogen protection, when reactor temperature rises to 240 ℃, adding 0.017g tosic acid is in reactor and keep this temperature range reaction 5h, makes the dissaving structure polymkeric substance;
(2) after step (1) reaction is finished, the 217.24g propylene glycol is added in the aforesaid reaction vessel, when reactor temperature rises to 170 ℃, keep this thermotonus 10h and simultaneously described reactor is vacuumized the water that generates with except dereaction, then described reactor temperature is risen to 230 ℃ and keep this thermotonus 10h, make the hyperbranched poly ester polyol;
Product polyester polyol after reaction finishes to step (2) is tested, and test result is as follows: acid number is 0.31mgKOH/g, and hydroxyl value is 90mgKOH/g, and moisture is 0.01623%, and chromatic number is 20 ~ 30APHA.
Embodiment 4
(1) selection has the reactor of agitator and nitrogen inlet, 134.17g TriMethylolPropane(TMP), 584.56g hexanodioic acid are added in the reactor, begin heating, treat to begin to stir after the above-mentioned reactants dissolved, when reactor temperature rises to 180 ℃, feed nitrogen protection, when reactor temperature rises to 240 ℃, adding 0.020g tosic acid is in reactor and keep this temperature range reaction 5h, makes the dissaving structure polymkeric substance;
(2) after step (1) reaction is finished, the 248.27g propylene glycol is added in the aforesaid reaction vessel, when reactor temperature rises to 150 ℃, keep this thermotonus 10h and simultaneously described reactor is vacuumized the water that generates with except dereaction, then described reactor temperature is risen to 220 ℃ and keep this thermotonus 15h, make the hyperbranched poly ester polyol;
Product polyester polyol after reaction finishes to step (2) is tested, and test result is as follows: acid number is 0.42mgKOH/g, and hydroxyl value is 90mgKOH/g, and moisture is 0.01702%, and chromatic number is 20 ~ 30APHA.
Carry out performance comparison with the conventional polyurethanes sole that adopts the preparation of conventional polyester polyvalent alcohol at the bottom of will adopting the hyperbranched poly ester polyol of preparing among the embodiment to prepare polyurethane shoe below, two kinds of polyester polyol differences that the urethane preparation of soles just adopts, a kind of is hyperbranched poly ester polyol among the embodiment, another kind is the conventional polyester polyvalent alcohol, and other starting material are all identical, preparation method at the bottom of two kinds of polyurethane shoes adopts the ordinary method preparation, and test result sees Table 1.
Table 1 for the polyurethane shoe of the hyperbranched poly ester polyol preparation of adopting the embodiment preparation at the bottom of with the performance comparison of conventional polyurethanes sole
| Sample | Density (g/cm 3） | Hardness (JISA) | Alternating bending tests (inferior) (23 ℃ flawless) |
| Conventional | 0.38 | 65 | Have for 50,000 times unusual |
| Embodiment 1 | 0.30 | 77 | 50,000 times no abnormal |
| Embodiment 2 | 0.31 | 70 | 50,000 times no abnormal |
| Embodiment 3 | 0.29 | 80 | 50,000 times no abnormal |
| Embodiment 4 | 0.30 | 82 | 50,000 times no abnormal |
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this art can understand content of the present invention and is implemented; can not limit protection scope of the present invention with this; and the invention is not restricted to the embodiments described; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed within protection scope of the present invention.
Claims (6)
1. a hyperbranched poly ester polyol is characterized in that, the structural formula of described hyperbranched poly ester polyol is:
Wherein, R is (CH
2)
a, 1≤a≤10; R
1Be (CH
2)
b, 1≤b≤10; A, b is natural number.
2. the preparation method of a hyperbranched poly ester polyol as claimed in claim 1 is characterized in that, described preparation method may further comprise the steps:
(1) preparation of dissaving structure polymkeric substance
Percentage composition meter by weight, TriMethylolPropane(TMP) with 10% ~ 25%, the acid of 45% ~ 65% organic multicomponent add in the reactor, begin heating, treat to begin to stir after the above-mentioned reactants dissolved, when described reactor temperature rises to 170 ℃ ~ 200 ℃, feed nitrogen protection, when described reactor temperature rises to 220 ℃ ~ 250 ℃, the catalyzer of adding 0.001% ~ 0.003% is in described reactor and keep this temperature range reaction 3h ~ 7h, makes the dissaving structure polymkeric substance;
(2) preparation of hyperbranched poly ester polyol
Percentage composition meter by weight, after step (1) reaction is finished, organic polyhydric alcohol with 15% ~ 30% adds in the aforesaid reaction vessel, when described reactor temperature rises to 120 ℃ ~ 170 ℃, keep this temperature range reaction 5h ~ 10h and simultaneously described reactor is vacuumized the water that generates with except dereaction, then described reactor temperature is risen to 200 ℃ ~ 250 ℃ and keep this temperature range reaction 10h ~ 24h, make the hyperbranched poly ester polyol;
More than the percentage composition of each component with the weight of component in component in the step (1) and the step (2) be 100% to calculate.
3. preparation method according to claim 2 is characterized in that, in the step (1), described organic multicomponent acid is the polyprotonic acid of two functionality, a kind of in the diacid of selecting oneself, terephthalic acid, the phthalic acid.
4. preparation method according to claim 2 is characterized in that, in the step (1), described catalyzer is a kind of in the vitriol oil, tosic acid, tetrabutyl titanate, titanium isopropylate, the sulfur oxychloride.
5. preparation method according to claim 2 is characterized in that, in the step (2), described organic polyhydric alcohol is the polyvalent alcohol of two functionality, is selected from a kind of in ethylene glycol, Diethylene Glycol, propylene glycol, neopentyl glycol, the methyl propanediol.
6. the application of hyperbranched poly ester polyol according to claim 1 at the bottom of the polyurethane shoe.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310184982.XA CN103275305B (en) | 2013-05-17 | 2013-05-17 | A kind of hyperbranched poly ester polyol for polyurethane shoe-sole and preparation method thereof |
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|---|---|---|---|
| CN201310184982.XA CN103275305B (en) | 2013-05-17 | 2013-05-17 | A kind of hyperbranched poly ester polyol for polyurethane shoe-sole and preparation method thereof |
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| CN103275305B CN103275305B (en) | 2015-08-26 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315441A (en) * | 2015-12-02 | 2016-02-10 | 威海晨源分子新材料有限公司 | Application of fatty acid modified hyperbranched polyester to plastic processing |
| CN111234159A (en) * | 2018-11-29 | 2020-06-05 | 中国石油化工股份有限公司 | Triple shape memory polymer and preparation method and application thereof |
| CN112094398A (en) * | 2020-09-25 | 2020-12-18 | 江苏登科聚氨酯材料有限公司 | High-stain-resistance thermoplastic polyurethane elastomer and preparation method thereof |
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| WO1999003908A1 (en) * | 1997-07-16 | 1999-01-28 | E.I. Du Pont De Nemours And Company | Hydroxy-functional oligomers for high solids coatings |
| WO2003055930A1 (en) * | 2001-12-21 | 2003-07-10 | Dow Global Technologies Inc. | Tertiary amine modified polyols and polyurethane products made therefrom |
| CN1961016A (en) * | 2004-05-31 | 2007-05-09 | 巴斯福股份公司 | Low-density polyurethane foam materials and their use in shoe soles |
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2013
- 2013-05-17 CN CN201310184982.XA patent/CN103275305B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1999003908A1 (en) * | 1997-07-16 | 1999-01-28 | E.I. Du Pont De Nemours And Company | Hydroxy-functional oligomers for high solids coatings |
| WO2003055930A1 (en) * | 2001-12-21 | 2003-07-10 | Dow Global Technologies Inc. | Tertiary amine modified polyols and polyurethane products made therefrom |
| CN1961016A (en) * | 2004-05-31 | 2007-05-09 | 巴斯福股份公司 | Low-density polyurethane foam materials and their use in shoe soles |
Non-Patent Citations (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315441A (en) * | 2015-12-02 | 2016-02-10 | 威海晨源分子新材料有限公司 | Application of fatty acid modified hyperbranched polyester to plastic processing |
| CN111234159A (en) * | 2018-11-29 | 2020-06-05 | 中国石油化工股份有限公司 | Triple shape memory polymer and preparation method and application thereof |
| CN111234159B (en) * | 2018-11-29 | 2022-01-04 | 中国石油化工股份有限公司 | Triple shape memory polymer and preparation method and application thereof |
| CN112094398A (en) * | 2020-09-25 | 2020-12-18 | 江苏登科聚氨酯材料有限公司 | High-stain-resistance thermoplastic polyurethane elastomer and preparation method thereof |
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| CN103275305B (en) | 2015-08-26 |
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