CN106189195A - A kind of polyurethane material based on poly-carbonic acid 1,3 propylene glycol ester polyhydric alcohol and preparation method thereof - Google Patents

A kind of polyurethane material based on poly-carbonic acid 1,3 propylene glycol ester polyhydric alcohol and preparation method thereof Download PDF

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Publication number
CN106189195A
CN106189195A CN201610567144.4A CN201610567144A CN106189195A CN 106189195 A CN106189195 A CN 106189195A CN 201610567144 A CN201610567144 A CN 201610567144A CN 106189195 A CN106189195 A CN 106189195A
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parts
poly
carbonic acid
solution
microcapsule
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黄伟
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • 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
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

nullThe present invention is open a kind of based on poly-carbonic acid 1,The polyurethane material of 3 propylene glycol ester polyhydric alcohol，It is made up of the raw material of following weight portion: polyether polyol 60 70 parts，Poly-carbonic acid 1,3 propylene glycol ester polyhydric alcohol 10 20 parts，Toluene di-isocyanate(TDI) 30 45 parts，Bamboo charcoal powder 15 25 parts，Chitosan 56 parts，Activated carbon 13 parts，Sodium alginate 13 parts，13 parts of gelatin，Sucrose fatty ester 10 15 parts，3% calcium chloride solution 58 parts，Flos Lonicerae quintessence oil 0.1 0.3 parts，Angelica essential oil 0.1 0.3 parts，Dibutyl tin laurate 24 parts，1,3 propylene glycol 35 parts，Foaming agent CFA A8 0.5 2 parts，Acetic acid solution 10 20 parts，Acetic acid 0.5 1 parts，Polycarbodiimide 1.5 2 parts，Water is appropriate，Appropriate amount of ethanol.The polyurethane material of the present invention has good permeability, antibacterial and deodouring effect, wearability.

Description

A kind of polyurethane material based on poly-carbonic acid 1,3-propylene glycol ester polyhydric alcohol and preparation thereof Method
Technical field
The present invention relates to footwear material technical field, be specifically related to a kind of poly-ammonia based on poly-carbonic acid 1,3-PD ester polyol Ester material and preparation method thereof.
Background technology
Footwear wear one of the advanced subject that comfortableness research is modern shoe-making field, it is people's living standard Inevitable outcome after raising, has important theory and realistic meaning.Along with China expand domestic demand, the reality of the policy that boosts consumption Execute, the expansion of middle class's quantity and the quickening of urbanization process, the consumption of footwear preferable to quality, fashionable in style and Demand also will increase steadily.Meanwhile, new and high technology is maked rapid progress, and new technique, new product emerge in an endless stream, thus promote new material Development and renewal.The successful Application of new material will bring unexpected achievement, in this process, vamp to shoe industry The heat-moisture transmission performance of material, is primary condition and the key factor affecting comfortableness.
It is good that polyurethane elastomer has shock-absorbing capacity, light weight, the feature such as wear-resisting, anti-skidding, good processability, it has also become shoemaking A kind of important footwear synthetic material in industry, can be used for manufacturing the fortune merit footwear of spike, golf, football etc., sole, footwear With, toe-cap, and skiing boots, safety shoe, playshoes etc..Polyurethane material for footwear material has casting type micro-pore elastomer and heat Plastic polyurethane elastomers etc., based on micro-pore elastomer sole.Microporous polyurethane elastomer light weight, wearability is the best, and Extrudate density is low, more light than traditional rubber-sole and PVC footwear material, and design can be diversified, also can be in injection moulding Add thermal decomposition foaming agent, producing foamed TPU flexible shoes material.
Huang Guoqing et al., in its a kind of embedding in situ microcapsule essence Quality Research one literary composition delivered, utilizes the most poly- Legal prepared essence content is the microcapsule of 32.5%, and its particle diameter is 1-4 μm, is substantially required for adding in this type of preparation process Formaldehyde generates performed polymer, does not reaches the requirement of environmental protection.Additionally Wang Junhua et al. is in the development of its Fragrant Microcapsule with Health-Care Effect delivered And in application one literary composition in textile, use interfacial polymerization is prepared for polyurethane for wall material, lavandula angustifolia as core Aroma finishing agent, bag load rate reaches about 80%, and delicate fragrance is still after 3 months.
Inspired by this, develop a kind of good permeability for footwear material, can the compound polyurethane material of deodorization.
Summary of the invention
The technical problem that present invention mainly solves is to provide a kind of poly-ammonia based on poly-carbonic acid 1,3-propylene glycol ester polyhydric alcohol Ester material and preparation method thereof.
The technical problem to be solved, is achieved through the following technical solutions:
A kind of polyurethane material based on poly-carbonic acid 1,3-PD ester polyol, is made up of the raw material of following weight portion: polyethers Polyhydric alcohol 60-70 part, poly-carbonic acid 1,3-PD ester polyol 10-20 part, toluene di-isocyanate(TDI) 30-45 part, bamboo charcoal powder 15- 25 parts, chitosan 5-6 part, activated carbon 1-3 part, sodium alginate 1-3 part, gelatin 1-3 part, sucrose fatty ester 10-15 part, 3% chlorination Calcium solution 5-8 part, Flos Lonicerae quintessence oil 0.1-0.3 part, angelica essential oil 0.1-0.3 part, dibutyl tin laurate 2-4 part, 1,3- Propylene glycol 3-5 part, foaming agent CFA-A8 0.5-2 part, acetic acid solution 10-20 part, acetic acid 0.5-1 part, polycarbodiimide 1.5- 2 parts, water is appropriate, appropriate amount of ethanol.
Specifically comprise the following steps that
(1) under room temperature, take chitosan and join in acetic acid solution, be sufficiently stirred for making chitosan be completely dissolved, be subsequently adding bamboo charcoal Powder, activated carbon, be sufficiently stirred for 2-3 hour, furnishing pasty state, places 12-20 hour, then at pelletize made on the machine spherical particle, Dry in drying baker, standby；
(2) preparation of microcapsule:
1., the preparation of wall material: by stirring in sodium alginate soln, gelatin solution addition container, obtain wall material solution；
2., emulsifying: add sucrose fatty ester in wall material solution, be uniformly mixed, add core Flos Lonicerae quintessence oil, Radix Angelicae Sinensis Quintessence oil was in 10000-20000rmp high speed shear emulsifying 5-15 minute；
3., the solidification of microcapsule: under conditions of being stirred continuously, in emulsion add vinegar acid-conditioning solution pH be acidity, It is simultaneously introduced 3% calcium chloride solution, after being placed in ice-water bath stirring 50-80 minute, stands, treat that microcapsule settles；
4., post processing: incline supernatant, filters, is washed to neutrality, then with absolute ethanol washing, be drying to obtain Flos Lonicerae quintessence oil, Angelica essential oil microcapsule；
(3), during microcapsule prepared by spherical particle step (1) obtained and step (2) adds stirred tank, polyether polyols is added Surplus stock beyond alcohol, poly-carbonic acid 1,3-PD ester polyol and removing toluene di-isocyanate(TDI), with 800-1500rpm Speed stir to mix homogeneously, obtain compound；
(4) toluene di-isocyanate(TDI) is joined the compound that step (3) obtains, stir 20-with the speed of 2000-3000rpm 60 seconds, cast note was in scribbling releasing agent in advance and being preheated to the mould of 40-50 DEG C immediately, after mold close, and 30-50 minute The rear demoulding, proceeds to ripening discharging in 7-9 hour at 60-90 DEG C in baking oven, obtains a kind of polynary based on poly-carbonic acid 1,3-PD ester The polyurethane material of alcohol.
Wherein, in the preparation of described step (2) microcapsule wall material solution be concentration be the sodium alginate soln of 1%-3%, The gelatin solution of 4%-7%.
A kind of based on poly-carbonic acid 1,3-PD ester polyol the polyurethane material of the present invention, compared with prior art has Have the following advantages:
(1) present invention utilizes microcapsule technology to prepare with Chinese herbal medicine Flos Lonicerae, when being classified as core, and sodium alginate, gelatin are wall material The microcapsule of delicate fragrance deodorization, not only keep the delicate fragrance deodorization character of core materials but also can slowly discharge core materials, prolongation effect Time, the compatibility with polyurethane material can be improved so that antibacterial and deodouring effect of compound polyurethane material is notable simultaneously；
(2) using bamboo charcoal, activated carbon and chitosan is raw material, prepares chitosan/compound porous adsorbent of bamboo charcoal-activated carbon, shell Polysaccharide can preferably be supported on bamboo charcoal, activated carbon, after blended combination uneven substantially, Honeycomb so that poly-ammonia Ester composite has good permeability, reaches deodouring effect simultaneously；
(3) polyurethane material based on poly-carbonic acid 1,3-PD ester polyol using the present invention to provide, uses poly-carbonization two Imines is as hydrolysis-resisting agent, and the polyurethane material of preparation has higher intensity and wearability, stronger anti-hydrolytic performance, uses Life-span is long, can be used for preparing at the bottom of Sports shoe sole, leather sole, casual soles, Labor protection shoes and military sole as material for sole of shoe Deng.Detailed description of the invention
A kind of polyurethane material based on poly-carbonic acid 1,3-PD ester polyol, by the raw material group of following weight portion (kilogram) Become: polyether polyol 85, poly-carbonic acid 1,3-PD ester polyol 15, toluene di-isocyanate(TDI) 40, bamboo charcoal powder 20, chitosan 5, Activated carbon 2, Polyethylene Glycol 1.5, sodium alginate 2, gelatin 1, sucrose fatty ester 12,3% calcium chloride solution 6, Flos Lonicerae quintessence oil 0.2, Angelica essential oil 0.2, dibutyl tin laurate 3,1,3-PD 4, foaming agent CFA-A8 1, acetic acid solution 15, acetic acid 1, poly- Carbodiimides 2, water is appropriate, appropriate amount of ethanol.
Specifically comprise the following steps that
(1) under room temperature, take chitosan and join in acetic acid solution, be sufficiently stirred for making chitosan be completely dissolved, be subsequently adding bamboo charcoal Powder, activated carbon, be sufficiently stirred for 3 hours, furnishing pasty state, places 15 hours, then at pelletize made on the machine spherical particle, is being dried Dry in case, standby；
(2) preparation of microcapsule:
1., the preparation of wall material: by stirring in sodium alginate soln, gelatin solution addition container, obtain wall material solution；
2., emulsifying: add sucrose fatty ester in wall material solution, be uniformly mixed, add core Flos Lonicerae quintessence oil, Radix Angelicae Sinensis Quintessence oil was in 15000rmp high speed shear emulsifying 10 minutes；
3., the solidification of microcapsule: under conditions of being stirred continuously, in emulsion add vinegar acid-conditioning solution pH be acidity, It is simultaneously introduced 3% calcium chloride solution, after being placed in ice-water bath stirring 60 minutes, stands, treat that microcapsule settles；
4., post processing: incline supernatant, filters, is washed to neutrality, then with absolute ethanol washing, be drying to obtain Flos Lonicerae quintessence oil, Angelica essential oil microcapsule；
(3), during microcapsule prepared by spherical particle step (1) obtained and step (2) adds stirred tank, polyether polyols is added Surplus stock beyond alcohol, poly-carbonic acid 1,3-PD ester polyol and removing toluene di-isocyanate(TDI), with the speed of 1000rpm Degree stirring, to mix homogeneously, obtains compound；
(4) toluene di-isocyanate(TDI) is joined the compound that step (3) obtains, stir 40 seconds with the speed of 2500rpm, immediately Cast note is in scribbling releasing agent in advance and being preheated to the mould of 45 DEG C, after mold close, and the demoulding after 40 minutes, proceed to baking oven In ripening discharging in 8 hours at 80 DEG C, obtain a kind of polyurethane material based on poly-carbonic acid 1,3-PD ester polyol.
Wherein, in the preparation of above-mentioned step (2) microcapsule wall material solution be concentration be the sodium alginate soln of 2%, 5% Gelatin solution.
Product checking data of the present invention: deodoriging properties is excellent, good air permeability, radially stretch breaking strength/broadwise stretch breaking strength ＞ 435N/3CM, footpath/filling-tear resistance ＞ 29N, degradation does not ftractures.

Claims (3)

1. a polyurethane material based on poly-carbonic acid 1,3-PD ester polyol, it is characterised in that by following weight portion Raw material forms: polyether polyol 60-70 part, poly-carbonic acid 1,3-PD ester polyol 10-20 part, toluene di-isocyanate(TDI) 30- 45 parts, bamboo charcoal powder 15-25 part, chitosan 5-6 part, activated carbon 1-3 part, sodium alginate 1-3 part, gelatin 1-3 part, sucrose fatty ester 10-15 part, 3% calcium chloride solution 5-8 part, Flos Lonicerae quintessence oil 0.1-0.3 part, angelica essential oil 0.1-0.3 part, tin dilaurate two fourth Base stannum 2-4 part, 1,3-PD 3-5 part, foaming agent CFA-A8 0.5-2 part, acetic acid solution 10-20 part, acetic acid 0.5-1 part is poly- Carbodiimides 1.5-2 part, water is appropriate, appropriate amount of ethanol.
2. according to the preparation of a kind of based on poly-carbonic acid 1,3-propylene glycol ester polyhydric alcohol the polyurethane material described in claims 1 Method, it is characterised in that specifically comprise the following steps that
(1) under room temperature, take chitosan and join in acetic acid solution, be sufficiently stirred for making chitosan be completely dissolved, be subsequently adding bamboo charcoal Powder, activated carbon, be sufficiently stirred for 2-3 hour, furnishing pasty state, places 12-20 hour, then at pelletize made on the machine spherical particle, Dry in drying baker, standby；
(2) preparation of microcapsule:
1., the preparation of wall material: by stirring in sodium alginate soln, gelatin solution addition container, obtain wall material solution；
2., emulsifying: add sucrose fatty ester in wall material solution, be uniformly mixed, add core Flos Lonicerae quintessence oil, Radix Angelicae Sinensis Quintessence oil was in 10000-20000rmp high speed shear emulsifying 5-15 minute；
3., the solidification of microcapsule: under conditions of being stirred continuously, in emulsion add vinegar acid-conditioning solution pH be acidity, It is simultaneously introduced 3% calcium chloride solution, after being placed in ice-water bath stirring 50-80 minute, stands, treat that microcapsule settles；
4., post processing: incline supernatant, filters, is washed to neutrality, then with absolute ethanol washing, be drying to obtain Flos Lonicerae quintessence oil, Angelica essential oil microcapsule；
(3), during microcapsule prepared by spherical particle step (1) obtained and step (2) adds stirred tank, polyether polyols is added Surplus stock beyond alcohol, poly-carbonic acid 1,3-PD ester polyol and removing toluene di-isocyanate(TDI), with 800-1500rpm Speed stir to mix homogeneously, obtain compound；
(4) toluene di-isocyanate(TDI) is joined the compound that step (3) obtains, stir 20-with the speed of 2000-3000rpm 60 seconds, cast note was in scribbling releasing agent in advance and being preheated to the mould of 40-50 DEG C immediately, after mold close, and 30-50 minute The rear demoulding, proceeds to ripening discharging in 7-9 hour at 60-90 DEG C in baking oven, obtains a kind of polynary based on poly-carbonic acid 1,3-PD ester The polyurethane material of alcohol.
3. according to the preparation of a kind of based on poly-carbonic acid 1,3-propylene glycol ester polyhydric alcohol the polyurethane material described in claims 2 Method, it is characterised in that in the preparation of step (2) microcapsule wall material solution be concentration be the sodium alginate soln of 1%-3%, 4%- The gelatin solution of 7%.
CN201610567144.4A 2016-07-19 2016-07-19 A kind of polyurethane material based on poly-carbonic acid 1,3 propylene glycol ester polyhydric alcohol and preparation method thereof Pending CN106189195A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111109254A (en) * 2019-12-19 2020-05-08 安徽伟创聚合材料科技有限公司 Novel polyurethane microcapsule environment-friendly pesticide and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111109254A (en) * 2019-12-19 2020-05-08 安徽伟创聚合材料科技有限公司 Novel polyurethane microcapsule environment-friendly pesticide and preparation method thereof

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Application publication date: 20161207