CN1114639C - Preparation of hard foamed poly urethane - Google Patents
Preparation of hard foamed poly urethane Download PDFInfo
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- CN1114639C CN1114639C CN 00117373 CN00117373A CN1114639C CN 1114639 C CN1114639 C CN 1114639C CN 00117373 CN00117373 CN 00117373 CN 00117373 A CN00117373 A CN 00117373A CN 1114639 C CN1114639 C CN 1114639C
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- starch
- ethylene glycol
- propylene oxide
- glucoside
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Abstract
The present invention relates to a preparation method for polyurethane hard foams. In the method, starch glycol glucoside propylene oxide polyether, butanediol, silicone oil, water, delaying catalysts and starch are uniformly and then are mixed with 90 to 110 parts by weight of poly-polyphenyl polymethyne polyisocyanate (PAPI); obtained products are cured for 3 to 10 hours at room temperature and then are cured for 10 to 20 minutes at 45 to 50 DEG C to obtain finished products. The polyurethane hard foam prepared by the method has the advantages of low-density, high tensile strength, strong pressure resistance, high bending resistant strength, low heat conduction coefficient, safe use, etc.
Description
The present invention relates to a kind of preparation method of hard foamed poly urethane.
In polyurethane field, there are deficiencies such as density height, thermal conductivity are low, bad mechanical property in present existing hard foamed poly urethane, can not satisfy the requirement of thermal insulation of materials aspect, mechanical properties.For example, disclose a kind of hard foamed poly urethane in " urethane foam body " (Chemical Industry Press, second edition, the 436th page) book of chief editors such as Fang Yusheng, its density is 38kg/m
3, thermal conductivity is that 26.1mw/mk, mean compressive strength are 121kPa, is usually used in refrigerator equipment with hard bubbling.Its main body is made up of the polyether glycol mixture of 35.5 weight parts and the isocyanic ester of 55 weight parts, adopts HCFC-123 (2-chlorine 3-vinyl fluoride) and HCFC-141b/CO
2(1-fluorine 2 vinylchlorid/carbonic acid gas) (mol ratio is 1: 1) made whipping agent and foamed and make, and its preparation method is a reaction injection molding process.This foams thermal conductivity is higher, bad mechanical property, and by HCFC-123 and HCFC-141b/CO
2The whipping agent system of forming has detrimentally affect to SBS (styrene-butadiene-styrene) plastics, the poly ageing resistance of high impact properties, must adjust the production line of refrigerator, in addition, HCFC-123 may make animal innocent tumour occur, has increased the insecurity of using.
The preparation method who the purpose of this invention is to provide a kind of new hard foamed poly urethane, the hard foamed poly urethane of this method preparation can overcome the deficiency of above-mentioned hard foamed poly urethane, advantage such as have that density is low, tensile strength is high, anti-pressure ability is strong, anti-flexural strength is big, thermal conductivity is low and safe in utilization.
The preparation method of hard foamed poly urethane of the present invention is as follows:
---starch ethylene glycol glycoside propylene oxide polyethers, butyleneglycol, silicone oil, water, delayed catalyst and starch are mixed by following parts by weight
Starch ethylene glycol glycoside propylene oxide polyethers 95～105
Butyleneglycol 8～10
Silicone oil 1.8～2.2
Water 0.1～3
Delayed catalyst 1.9～2.3
Starch 10～60
---add the poly-many phenyl polymethine polyisocyanates (PAPI) of 90～110 weight parts;
---products therefrom solidified between 45～50 ℃ 10～20 minutes through self-vulcanizing 3～10 hours, obtained product;
Wherein, starch ethylene glycol glycoside propylene oxide polyether viscosity is 9600～11000cp, and hydroxyl value is 400～420mgKOH/g; Required delayed catalyst mixes acquisition by trolamine and triethylenediamine in 3: 4 ratio (weight part); Required starch is W-Gum or potato starch, and weight in wet base part is 2～13%; The viscosity of PAPI is between 180～220cp (25 ℃), and average functionality is 2.3～2.7; Butyleneglycol, silicone oil are the commercially available prod; Water is deionized water.
Starch ethylene glycol glycoside propylene oxide polyethers also can be made by following method: mix the starch of 1 weight part (1) with the ethylene glycol of 4 weight parts, under 125～130 ℃, pH=4 condition, reacted 30～60 minutes, make the commentaries on classics glucoside reacting weight of ethylene glycol reach 0.75～0.84 mole of ethylene glycol/mole dehydrated glucose unit, obtain starch ethylene glycol glucoside thing, extract unnecessary ethylene glycol; (2) be to use the propylene oxide etherificate under 7.8～8.4 the alkaline condition in the pH value with starch ethylene glycol glucoside thing, the reaction times is 4.5～8 hours, and the etherificate rate is between 7.5～8.5 moles of propylene oxide/glucoside thing; (3) with reaction product process process for refining, obtain required starch ethylene glycol glycoside propylene oxide polyethers.
The present invention is a raw material with starch ethylene glycol glycoside propylene oxide polyethers, butyleneglycol, silicone oil, water, delayed catalyst, starch and poly-many phenyl polymethine polyisocyanates (PAPI), adopt full water foamed method to be prepared, the hard foamed poly urethane density that obtains is 29～37kg/m
3, thermal conductivity is that 23.1～26.1mw/mk, tensile strength are that 220～260kPa, ultimate compression strength are 150～230kPa.
The present invention has following difference and advantage:
(1) density of material is low, the tensile strength height, and anti-flexural strength is big, anti-pressure ability is strong, and thermal conductivity is low;
(2) preparation method is simple, need not specific equipment;
(3) method of the present invention is identical with existing full water foamed method aspect reaction conditions, reactions steps, and difference is that raw materials used prescription is different.
The invention will be further described below by embodiment.
Embodiment 1
The preparation of starch ethylene glycol glycoside propylene oxide polyethers: (1) mixes 1 kilogram the starch ethylene glycol with 4 kilograms, and reaction is 30 minutes under 130 ℃ of conditions, obtains starch ethylene glycol glucoside thing, extracts unnecessary ethylene glycol; (2) be to use the propylene oxide etherificate under 7.8 the alkaline condition in the pH value with the starch ethylene glycol glucoside thing of gained, controlling reaction time is 4.5 hours, and the etherificate rate is 7.5 moles of propylene oxide/mole glucoside thing; (3) with reaction product process process for refining, obtain required starch ethylene glycol glycoside propylene oxide polyethers.
The preparation of delayed catalyst:, obtain required delayed catalyst with trolamine and triethylenediamine mixed by 3: 4.
The preparation of hard foamed poly urethane: (1) is that 8.5% starch ethylene glycol glycoside propylene oxide polyethers, 8 kilograms butyleneglycol, 2 kilograms silicone oil, 3 kilograms water, 2 kilograms delayed catalyst and 10 kilograms starch mix in same container with 100 kilograms of water content; (2) add 100 kilograms PAPI; (3) products therefrom solidified 20 minutes between 45～50 ℃ through self-vulcanizing 3 hours, obtained hard foamed poly urethane of the present invention.
Products obtained therefrom is the white foam body, and its density is 37kg/m after measured
3, thermal conductivity is that 26.10m.W/ (m.K), tensile strength are that 260kPa, ultimate compression strength are 230kPa, meets this field industrial requirements.
Embodiment 2
The preparation of starch ethylene glycol glycoside propylene oxide polyethers: (1) mixes 1 kilogram the starch ethylene glycol with 4 kilograms, and reaction is 60 minutes under 125 ℃ of conditions, obtains starch ethylene glycol glucoside thing, extracts unnecessary ethylene glycol; (2) be to use the propylene oxide etherificate under 8.0 the alkaline condition in the pH value with the starch ethylene glycol glucoside thing of gained, controlling reaction time is 5 hours, and the etherificate rate is 8.0 moles of propylene oxide/mole glucoside thing; (3) with reaction product process process for refining, obtain required starch ethylene glycol glycoside propylene oxide polyethers.
The preparation of delayed catalyst: with embodiment 1.
The preparation of hard foamed poly urethane: the preparation method is with embodiment 1, and wherein the water content of starch is 3%, and filling a prescription is:
100 kilograms of starch ethylene glycol glycoside propylene oxide polyethers
9 kilograms of butyleneglycols
1.8 kilograms of silicone oil
3 kilograms in water
2 kilograms of delayed catalysts
10 kilograms of starch
90 kilograms of PAPI
Products therefrom solidified 10 minutes between 45～50 ℃ through self-vulcanizing 10 hours, and obtaining product is the white foam body, and its density is 31kg/m after measured
3, thermal conductivity is that 25.20m.W/ (m.K), tensile strength are that 254kPa, ultimate compression strength are 224kPa, meets this field industrial requirements.
Embodiment 3
The preparation of starch ethylene glycol glycoside propylene oxide polyethers: (1) mixes 1 kilogram the starch ethylene glycol with 4 kilograms, and reaction is 45 minutes under 128 ℃ of conditions, obtains starch ethylene glycol glucoside thing, extracts unnecessary ethylene glycol; (2) be to use the propylene oxide etherificate under 8.4 the alkaline condition in the pH value with the starch ethylene glycol glucoside thing of gained, controlling reaction time is 6 hours, and the etherificate rate is 8.5 moles of propylene oxide/mole glucoside thing; (3) with reaction product process process for refining, obtain required starch ethylene glycol glycoside propylene oxide polyethers.
The preparation of delayed catalyst: with embodiment 1.
The preparation of hard foamed poly urethane: with embodiment 1, the water content of starch is 2%, fills a prescription to be (kilogram):
Starch ethylene glycol glycoside propylene oxide polyethers 95
Butyleneglycol 10
Silicone oil 2
Water 3
Delayed catalyst 2
Starch 20
PAPI 110
Products therefrom solidified 15 minutes between 45～50 ℃ through self-vulcanizing 5 hours, and obtaining product is the white foam body, and its density is 32kg/m after measured
3, thermal conductivity is that 25.20m.W/ (m.K), tensile strength are that 250kPa, ultimate compression strength are 225kPa, meets this field industrial requirements.
Embodiment 4
The preparation of starch ethylene glycol glycoside propylene oxide polyethers: (1) mixes 1 kilogram the starch ethylene glycol with 4 kilograms, and reaction is 45 minutes under 125 ℃ of conditions, obtains starch ethylene glycol glucoside thing, extracts unnecessary ethylene glycol; (2) be to use the propylene oxide etherificate under 8.2 the alkaline condition in the pH value with the starch ethylene glycol glucoside thing of gained, controlling reaction time is 6 hours, and the etherificate rate is 8.5 moles of propylene oxide/mole glucoside thing; (3) with reaction product process process for refining, obtain required starch ethylene glycol glycoside propylene oxide polyethers.
The preparation of delayed catalyst: with embodiment 1.
The preparation of hard foamed poly urethane: the preparation method is with embodiment 1, and the water content of starch is 13%, fills a prescription to be (kilogram):
Starch ethylene glycol glycoside propylene oxide polyethers 105
Butyleneglycol 8
Silicone oil 2.2
Water 0.1
Delayed catalyst 2
Starch 30
PAPI 95
Products obtained therefrom is the white foam body, and its density is 31kg/m after measured
3, thermal conductivity is that 25.20m.W/ (m.K), tensile strength are that 240kPa, ultimate compression strength are 160kPa, meets this field industrial requirements.
Embodiment 5
The preparation of starch ethylene glycol glycoside propylene oxide polyethers: (1) mixes 1 kilogram the starch ethylene glycol with 4 kilograms, and reaction is 45 minutes under 130 ℃ of conditions, obtains starch ethylene glycol glucoside thing, extracts unnecessary ethylene glycol; (2) be to use the propylene oxide etherificate under 8.0 the alkaline condition in the pH value with the starch ethylene glycol glucoside thing of gained, controlling reaction time is 7 hours, and the etherificate rate is 8.0 moles of propylene oxide/mole glucoside thing; (3) with reaction product process process for refining, obtain required starch ethylene glycol glycoside propylene oxide polyethers.
The preparation of delayed catalyst: with embodiment 1.
The preparation of hard foamed poly urethane: with embodiment 1, the water content of starch is 6%, fills a prescription to be (kilogram):
Starch ethylene glycol glycoside propylene oxide polyethers 100
Butyleneglycol 10
Silicone oil 2
Water 0.1
Delayed catalyst 2
Starch 40
PAPI 95
Products obtained therefrom is the white foam body, and its density is 30.1kg/m after measured
3, thermal conductivity is that 25.20m.W/ (m.K), tensile strength are that 240kPa, ultimate compression strength are 170kPa, meets this field industrial requirements.
Embodiment 6
The preparation of starch ethylene glycol glycoside propylene oxide polyethers: (1) mixes 1 kilogram the starch ethylene glycol with 4 kilograms, and reaction is 45 minutes under 130 ℃ of conditions, obtains starch ethylene glycol glucoside thing, extracts unnecessary ethylene glycol; (2) be to use the propylene oxide etherificate under 8.2 the alkaline condition in the pH value with the starch ethylene glycol glucoside thing of gained, controlling reaction time is 8 hours, and the etherificate rate is 8.5 moles of propylene oxide/mole glucoside thing; (3) with reaction product process process for refining, obtain required starch ethylene glycol glycoside propylene oxide polyethers.
The preparation of delayed catalyst: with embodiment 1.
The preparation of hard foamed poly urethane: with embodiment 1, the water content of starch is 3%, fills a prescription to be (kilogram):
Starch ethylene glycol glycoside propylene oxide polyethers 100
Butyleneglycol 9
Silicone oil 2
Water 1.5
Delayed catalyst 2
Starch 50
PAPI 100
Products obtained therefrom is the white foam body, and its density is 29kg/m after measured
3, thermal conductivity is that 25.20m.W/ (m.K), tensile strength are that 235kPa, ultimate compression strength are 175kPa, meets this field industrial requirements.
Embodiment 7
The preparation of starch ethylene glycol glycoside propylene oxide polyethers: (1) mixes 1 kilogram the starch ethylene glycol with 4 kilograms, and reaction is 45 minutes under 130 ℃ of conditions, obtains starch ethylene glycol glucoside thing, extracts unnecessary ethylene glycol; (2) be to use the propylene oxide etherificate under 8.4 the alkaline condition in the pH value with the starch ethylene glycol glucoside thing of gained, controlling reaction time is 6 hours, and the etherificate rate is 8.5 moles of propylene oxide/mole glucoside thing; (3) with reaction product process process for refining, obtain required starch ethylene glycol glycoside propylene oxide polyethers.
The preparation of delayed catalyst: with embodiment 1.
The preparation of hard foamed poly urethane: the preparation method is with embodiment 1, and the water content of starch is 3%, fills a prescription to be (kilogram):
Starch ethylene glycol glycoside propylene oxide polyethers 100
Butyleneglycol 10
Silicone oil 2
Water 3
Delayed catalyst 2.3
Starch 60
PAPI 100
Products obtained therefrom is the white foam body, and its density is 31.3kg/m after measured
3, thermal conductivity is that 25.20m.W/ (m.K), tensile strength are that 220kPa, ultimate compression strength are 150kPa, meets this field industrial requirements.
Embodiment 8
The preparation of starch ethylene glycol glycoside propylene oxide polyethers: (1) mixes 1 kilogram the starch ethylene glycol with 4 kilograms, and reaction is 60 minutes under 125 ℃ of conditions, obtains starch ethylene glycol glucoside thing, extracts unnecessary ethylene glycol; (2) be to use the propylene oxide etherificate under 7.8 the alkaline condition in the pH value with the starch ethylene glycol glucoside thing of gained, controlling reaction time is 6 hours, and the etherificate rate is 7.5 moles of propylene oxide/mole glucoside thing; (3) with reaction product process process for refining, obtain required starch ethylene glycol glycoside propylene oxide polyethers.
The preparation of delayed catalyst: with embodiment 1.
The preparation of hard foamed poly urethane: the preparation method is with embodiment 1, and the water content of starch is 9%, fills a prescription to be (kilogram):
Starch ethylene glycol glycoside propylene oxide polyethers 100
Butyleneglycol 9
Silicone oil 2
Water 3
Delayed catalyst 1.9
Starch 10
PAPI 100
Products obtained therefrom is the white foam body, and its density is 34kg/m after measured
3, thermal conductivity is 23.10m.W/ (m.K), tensile strength is that 255kPa, ultimate compression strength are 230kPa, meets this field industrial requirements.
Claims (1)
1, a kind of preparation method of hard foamed poly urethane is characterized in that comprising the steps:
---starch ethylene glycol glycoside propylene oxide polyethers, butyleneglycol, silicone oil, water, delayed catalyst and starch are mixed by following parts by weight
Starch ethylene glycol glycoside propylene oxide polyethers 95～105
Butyleneglycol 8～10
Silicone oil 1.8～2.2
Water 0.1～3
Delayed catalyst 1.9～2.3
Starch 10～60
---add the poly-many phenyl polymethine polyisocyanates (PAPI) of 90～110 weight parts;
---products therefrom solidified between 45～50 ℃ 10～20 minutes through self-vulcanizing 3～10 hours, obtained product; Wherein, starch ethylene glycol glycoside propylene oxide polyether viscosity is 9600～11000cp, and hydroxyl value is 400～420mgKOH/g; Required delayed catalyst mixes acquisition by trolamine and triethylenediamine in 3: 4 ratio (weight part); Required starch is W-Gum or potato starch, and weight in wet base part is 2～13%; The viscosity of PAPI is between 180～220cp (25 ℃), and average functionality is 2.3～2.7; Butyleneglycol, silicone oil are the commercially available prod; Water is deionized water; Starch ethylene glycol glycoside propylene oxide polyethers is made by following method: mix the starch of 1 weight part (1) with the ethylene glycol of 4 weight parts, under 125～130 ℃, pH=4 condition, reacted 30～60 minutes, make the commentaries on classics glucoside reacting weight of ethylene glycol reach 0.75～0.84 mole of ethylene glycol/mole dehydrated glucose unit, obtain starch ethylene glycol glucoside thing, extract unnecessary ethylene glycol; (2) be to use the propylene oxide etherificate under 7.8～8.4 the alkaline condition in the pH value with starch ethylene glycol glucoside thing, the reaction times is 4.5～8 hours, and the etherificate rate is between 7.5～8.5 moles of propylene oxide/glucoside thing; (3) with reaction product process process for refining, obtain required starch ethylene glycol glycoside propylene oxide polyethers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00117373 CN1114639C (en) | 2000-08-30 | 2000-08-30 | Preparation of hard foamed poly urethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00117373 CN1114639C (en) | 2000-08-30 | 2000-08-30 | Preparation of hard foamed poly urethane |
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| CN1288904A CN1288904A (en) | 2001-03-28 |
| CN1114639C true CN1114639C (en) | 2003-07-16 |
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| CN 00117373 Expired - Fee Related CN1114639C (en) | 2000-08-30 | 2000-08-30 | Preparation of hard foamed poly urethane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101238161B (en) * | 2005-08-12 | 2011-07-06 | 三井化学株式会社 | Composition for polyurethane foam, polyurethane foam obtained from the composition, and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2904929A1 (en) * | 2013-03-12 | 2014-10-09 | 3M Innovative Properties Company | Removal of chloramine and mercury from aqueous solutions |
| CN106969257A (en) * | 2017-04-12 | 2017-07-21 | 酷泰克保温科技江苏有限公司 | A kind of construction technology of LNG storage tank heat-insulation system |
| CN107814900A (en) * | 2017-11-21 | 2018-03-20 | 广西吉宽太阳能设备有限公司 | A kind of solar energy polyurethane heat insulation material and preparation method thereof |
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2000
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101238161B (en) * | 2005-08-12 | 2011-07-06 | 三井化学株式会社 | Composition for polyurethane foam, polyurethane foam obtained from the composition, and use thereof |
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| Publication number | Publication date |
|---|---|
| CN1288904A (en) | 2001-03-28 |
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