CN106565935A - Preparation method of dimer acid polyol and application thereof in polyurethane foam - Google Patents
Preparation method of dimer acid polyol and application thereof in polyurethane foam Download PDFInfo
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- CN106565935A CN106565935A CN201610971925.XA CN201610971925A CN106565935A CN 106565935 A CN106565935 A CN 106565935A CN 201610971925 A CN201610971925 A CN 201610971925A CN 106565935 A CN106565935 A CN 106565935A
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- dimeric dibasic
- dibasic acid
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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
- C08G18/70—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
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/10—Water or water-releasing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a preparation method of dimer acid polyol and an application thereof in polyurethane foam, and belongs to the field of biological source high polymer materials. According to the preparation method of the dimer acid polyol, provided by the invention, dimer acid and propanetriol are used as raw materials, and bis(lauroyloxy)dioctyl tin, zinc acetate, tetrabutyl titanate and the like are used as catalysts to perform an esterification reaction to obtain polyhydroxyl polyol. The dimer acid polyol provided by the invention has the advantages that the raw materials are wide in source, can be extracted from common plants, and are nontoxic and harmless. The polyurethane foam prepared by using the dimer acid polyol has the characteristics of good mechanical properties and excellent thermal insulation property.
Description
Technical field
The present invention relates to the synthesis and the application in polyurethane foam of a kind of bio-based source dimeric dibasic acid polyhydric alcohol, belong to
Can biogenetic derivation polymeric material field.
Background technology
Polyurethane foam is the current best insulation material of performance in the world, and main chain is containing-NHCOO-constitutional repeating unit
One birds of the same feather flock together compound, english abbreviation PU.It is polymerized with hydroxy compounds by isocyanates (monomer), its production process is by many
First alcohol and isocyanates under appropriate ambient temperature, are obtained containing carbamate groups with auxiliary agents such as catalyst, foaming agent
Closed-cell foam.The polyhydric alcohol that polyurethane foam is used is mainly polyether polyol and PEPA, and it is extracted by oil, and
Oil is non-renewable energy resources.In the face of the constantly progressive situation of current resource worsening shortages and society, this and contemporary sustainable development
The demand of exhibition is disagreed with target.
Meanwhile, people are increasing to the demand of macromolecular material, the requirement of performance also more and more higher.However, due to
The not readily degradable of macromolecular material so as to while being widely used, also brought a series of environmental pollution and
Ecological problem, therefore the Biodegradable material of research environment friendly as early as possible is further urgent.
Dimeric dibasic acid is a kind of biodegradable polymer of bio-based source, is the product of natural oil, with poison
Property is low, wide material sources and it is renewable the advantages of.Simultaneously because dimeric dibasic acid has the larger nonpolar hydroxyl of two carboxyls and two, its
The Long carbon chain of the branched structure of height and 36 carbon atom compositions makes it have good thermal stability, the flexibility of height
With superpower hydrophobicity, it is excellent that the dimeric dibasic acid polyhydric alcohol that itself and polyols preparation are obtained can give polyurethane foam mechanical property
Different, thermally-stabilised strong, water-tolerant, the low advantage of heat conductivity.
The content of the invention
It is an object of the invention to provide a kind of bio-based source contains the preparation method of polyhydroxy based dimeric acid polyhydric alcohol, lead to
Cross and synthesize this dimeric dibasic acid polyhydric alcohol, by use of the petroleum replacing polylol in polyurethane foam, to environmental protection, drop
Low stain, reaches the purpose of sustainable development.
To achieve these goals, the technical scheme is that：
A kind of dimeric dibasic acid polyhydric alcohol containing polyhydroxy bio-based source, it is obtained by following raw materials according is synthetically prepared：
Dimeric dibasic acid and glycerol molar ratio are 1：1-1：3.
Catalyst amount is the 0.1%-2% of dimeric dibasic acid quality.
Wherein, catalyst is dibutyl tin laurate, butyl titanate, zinc acetate etc..
A kind of preparation method of above-mentioned dimeric dibasic acid polyhydric alcohol containing polyhydroxy bio-based source, will enter by the following method
OK：
(1) weigh：Dimeric dibasic acid and glycerol are weighed according to above-mentioned ratio, is subsequently adding and is accounted for dimeric dibasic acid quality
The catalyst of 0.1%-2%；
(2) preparation of dimeric dibasic acid polyhydric alcohol：Reaction in step (1) is passed through into nitrogen, mechanical agitation rotating speed is 500r/
Min, while, to exclude the water that reaction is generated, making reaction carry out to positive direction plus water knockout drum and condensing tube in side, arranges temperature
140～160 DEG C of degree, measures acid number, and when acid number is reached below 1, its reaction is complete, can be dried product and removed with stopped reaction
Moisture, obtained product dimeric dibasic acid polyhydric alcohol.
The hydroxyl value scope of above-mentioned dimeric dibasic acid polyhydric alcohol is 250-600mg KOH/g.
By above-mentioned dimeric dibasic acid polyols preparation polyurethane foam, its formula for preparing is：
100 parts of dimeric dibasic acid polyhydric alcohol,
20 parts of foaming agent,
1 part of catalyst,
2 parts of silicone oil,
1 part of water.
According to isocyanate index 1.1 add isocyanates in a certain proportion of isocyanates, i.e. polyisocyanates and
The mol ratio of hydroxyl is 1.1 in polyhydric alcohol:1.
Wherein foaming agent is a fluorine dichloroethanes (HCFC-141b)；
Wherein catalyst be N, N- dimethyl cyclohexyl amines (PC-8)；
Wherein silicone oil be AK8805, a kind of silicon-carbon bond non-hydrolytic type polysiloxane-polyether copolymer；
Wherein water is, as a kind of CBA, to produce atmospheric carbon dioxide；
Isocyanates are polymethylene multi-phenenyl isocyanate, model PM-200.
A kind of method of above-mentioned polyhydroxy biology based dimeric acid polyols preparation polyurethane foam, enters according to following steps
OK：
The mixing of white material：Dimeric dibasic acid polyhydric alcohol, catalyst, foaming agent, water, silicone oil etc. are weighed according to aforementioned proportion
In 250ml plastic cups, 3min is stirred under mechanical agitation (700r/min) to uniform state, treat that lower step is used.
The white material quantitative isocyanates being rapidly added in (2), under mechanical agitation (2500r/min) stirring 7～
9s, in being quickly poured into mould, free foaming obtains the polyurethane foam of bio-based source, and foam is prepared according to standard cutting
Batten, finally, carries out the test of properties.
The present invention has advantages below：
The polyurethane foam of the present invention, the dimeric dibasic acid polyol starting material wide material sources that it is adopted, industrial dimeric dibasic acid is former
Material, is nearly all C 18 unsaturated fatty acid, such as cotton oil acid, Semen sojae atricolor Oleic acid, sunflower seed oil fatty acids etc., can be carried from plant
Take, reduce the dependency to oil.
The present invention voluntarily prepares dimeric dibasic acid polyhydric alcohol and replaces commercially available polyethers many on the basis of prepared by forefathers' polyurethane foam
First alcohol 4110, is optimized to the system of dimeric dibasic acid polyols preparation polyurethane foam, and to its prepared polyurethane foam
Properties have carried out systematic research.
The present invention can prepare under different conditions expected dimeric dibasic acid polyhydric alcohol, the dimeric dibasic acid polyhydric alcohol for obtaining
There is higher hydroxyl value and degree of functionality, the polyurethane foam prepared using the present invention has good mechanical property and excellent guarantor
Warm nature energy.
Specific embodiment
The present embodiment is only won some the concrete numerical value parameter in description in listed scope and is illustrated, as long as saying
In bright book it is listed within the scope of, can complete invent concrete steps.
Reference examples
30g polyether polyol 4110 is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding, 0.15g catalyst,
Then 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min adds PM-200 with isocyanate index 1.1,
7s is stirred under 2500r/min, mould is poured the mixture into, sample test, test result such as table 1 are cut out after ripening 24h.
Embodiment 1
169.8g dimeric dibasic acids and 27.6g glycerol are added in 500ml four-hole boiling flasks, then the February of Deca 0.17g
Dilaurylate, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 140
DEG C, stir 20h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test, test result are cut out after ripening 24h
Such as table 1.
Embodiment 2
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the February of Deca 0.17g
Dilaurylate, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 140
DEG C, stir 20h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 3
169.8g dimeric dibasic acids and 82.8g glycerol are added in 500ml four-hole boiling flasks, then the February of Deca 0.17g
Dilaurylate, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 140
DEG C, stir 20h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 4
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the February of Deca 1.70g
Dilaurylate, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 140
DEG C, stir 18.5h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 5
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the February of Deca 2.85g
Dilaurylate, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 140
DEG C, stir 18h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 6
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the February of Deca 3.40g
Dilaurylate, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 140
DEG C, stir 17h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 7
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the February of Deca 1.70g
Dilaurylate, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 150
DEG C, stir 17h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 8
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the February of Deca 1.70g
Dilaurylate, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 160
DEG C, stir 15h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 9
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the acetic acid of Deca 0.17g
Zinc, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, and oil bath pan is heated to into 160 DEG C, stirs 19h,
Measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 10
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the acetic acid of Deca 1.70g
Zinc, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, and oil bath pan is heated to into 160 DEG C, stirs 18h,
Measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 11
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the acetic acid of Deca 2.55g
Zinc, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 160 DEG C, stirring
17.5h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 12
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the acetic acid of Deca 3.40g
Zinc, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 160 DEG C, stirring
15.5h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 13
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the metatitanic acid of Deca 0.17g
Four butyl esters, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 160 DEG C, stirring
18.5h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 14
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the metatitanic acid of Deca 1.70g
Four butyl esters, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 160 DEG C, stirring
16h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 15
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the metatitanic acid of Deca 2.55g
Four butyl esters, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 160 DEG C, stirring
15h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 16
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the metatitanic acid of Deca 3.40g
Four butyl esters, in side nitrogen is passed through, and opposite side adds water knockout drum and condensation reflux unit, oil bath pan is heated to into 160 DEG C, stirring
13h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
Embodiment 17
169.8g dimeric dibasic acids and 55.2g glycerol are added in 500ml four-hole boiling flasks, then the February of Deca 0.17g
Dilaurylate, 0.85g zinc acetates, 0.85g butyl titanates are passed through nitrogen in side, and opposite side adds water knockout drum and cold
Solidifying reflux, by oil bath pan 160 DEG C are heated to, and stir 13h, measurement acid number and hydroxyl value.
The dimeric dibasic acid polyhydric alcohol of the above-mentioned preparations of 30g is weighed in the plastic cup of 250ml, 0.60g silicone oil is subsequently adding,
0.15g catalyst, 0.30g water, 6.00g 141b, mechanical agitation 3min under 700r/min, then with isocyanate index 1.1
PM-200 is added, under 2500r/min 7s is stirred, pour the mixture into mould, sample test is cut out after ripening 24h, its result is such as
Table 1.
The different formulations dimeric dibasic acid polyhydric alcohol performance of table 1 and its prepare polyurethane foam performance
The dimeric dibasic acid that high hydroxyl value and low acid number can be obtained by different preparation methoies is can be seen that by above-mentioned two table many
First alcohol, its polyurethane foam for preparing, with good mechanical property and excellent heat-insulating property.The dimeric dibasic acid of the present invention is more
First alcohol can be used as the succedaneum of commercially available polyether/polyester polyol, it is possible to decrease the dependency to oil.
Claims (6)
1. a kind of dimeric dibasic acid polyhydric alcohol containing polyhydroxy bio-based source, it is characterised in that synthetically prepared by following raw materials according
Arrive：
Dimeric dibasic acid and glycerol molar ratio are 1：1-1：3；
Catalyst amount is the 0.1%-2% of dimeric dibasic acid quality；
Wherein, catalyst is dibutyl tin laurate, butyl titanate, zinc acetate.
2. the preparation method of a kind of dimeric dibasic acid polyhydric alcohol containing polyhydroxy bio-based source described in claim 1, its feature
It is to carry out by the following method：
（1）Weigh：Dimeric dibasic acid and glycerol are weighed according to above-mentioned ratio, the 0.1%-2% for accounting for dimeric dibasic acid quality is subsequently adding
Catalyst；
（2）The preparation of dimeric dibasic acid polyhydric alcohol：By step（1）In reaction be passed through nitrogen, mechanical agitation rotating speed is 500r/min, together
When in side plus water knockout drum and condensing tube, to exclude the water that reaction is generated, reaction is carried out to positive direction, arrange temperature 140 ~
160 DEG C, acid number is measured, when acid number is reached below 1, its reaction is complete, can be dried product and remove moisture, system with stopped reaction
The product dimeric dibasic acid polyhydric alcohol for obtaining.
3. the preparation method of a kind of dimeric dibasic acid polyhydric alcohol containing polyhydroxy bio-based source according to claim 2, its
The hydroxyl value scope for being characterised by above-mentioned dimeric dibasic acid polyhydric alcohol is 250-600 mg KOH/g.
4. a kind of dimeric dibasic acid polyhydric alcohol containing polyhydroxy bio-based source described in claim 1 is used to prepare polyurethane foam
Method, it is characterised in that its formula is：
100 parts of dimeric dibasic acid polyhydric alcohol,
20 parts of foaming agent,
1 part of catalyst,
2 parts of silicone oil,
1 part of water；
Isocyanates in a certain proportion of isocyanates, i.e. polyisocyanates and polynary are added according to isocyanate index 1.1
The mol ratio of hydroxyl is 1.1 in alcohol:1.
5. a kind of dimeric dibasic acid polyhydric alcohol containing polyhydroxy bio-based source according to claim 4 is used to prepare polyurethane
The method of foam, wherein foaming agent are a fluorine dichloroethanes（HCFC-141b）；
Wherein catalyst be N, N- dimethyl cyclohexyl amines（PC-8）；
Wherein silicone oil be AK8805, a kind of silicon-carbon bond non-hydrolytic type polysiloxane-polyether copolymer；
Isocyanates are polymethylene multi-phenenyl isocyanate, model PM-200.
6. a kind of method of polyhydroxy biology based dimeric acid polyols preparation polyurethane foam according to claim 4, presses
Carry out according to following steps：
（1）The mixing of white material：Dimeric dibasic acid polyhydric alcohol, catalyst, foaming agent, water, silicone oil etc. are weighed according to aforementioned proportion
In 250ml plastic cups, in mechanical agitation（700r/min）Lower stirring 3min treats that lower step is used to uniform state；
（2）Quantitative isocyanates are rapidly added to（1）In white material, in mechanical agitation（2500r/min）7 ~ 9s of lower stirring,
In being quickly poured into mould, free foaming obtains the polyurethane foam of bio-based source, and according to standard cutting prepared by foam into sample
Bar, finally, carries out the test of properties.
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| CN114853977A (en) * | 2022-04-27 | 2022-08-05 | 盛鼎高新材料有限公司 | High-permeability high-elasticity polyurethane elastomer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107857871A (en) * | 2017-11-13 | 2018-03-30 | 常州大学 | A kind of preparation method of malic acid polyalcohol and its application in polyurethane foam |
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| CN109851836B (en) * | 2018-12-29 | 2021-06-15 | 浙江华江科技股份有限公司 | High-strength environment-friendly light polyurethane foam with hyperbranched polyester polyol as cross-linking agent and preparation method thereof |
| CN112225861A (en) * | 2020-10-30 | 2021-01-15 | 常州大学 | Visible light self-repairing high-strength waterborne polyurethane and preparation method thereof |
| CN112225861B (en) * | 2020-10-30 | 2022-03-01 | 常州大学 | Visible light self-repairing high-strength waterborne polyurethane and preparation method thereof |
| CN114853977A (en) * | 2022-04-27 | 2022-08-05 | 盛鼎高新材料有限公司 | High-permeability high-elasticity polyurethane elastomer and preparation method thereof |
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