CN110028645A - A kind of fast demoulding combined polyether and its polyurethane and preparation method - Google Patents
A kind of fast demoulding combined polyether and its polyurethane and preparation method Download PDFInfo
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- CN110028645A CN110028645A CN201910208103.XA CN201910208103A CN110028645A CN 110028645 A CN110028645 A CN 110028645A CN 201910208103 A CN201910208103 A CN 201910208103A CN 110028645 A CN110028645 A CN 110028645A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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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
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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
- C08G2101/00—Manufacture of cellular products
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of fast demoulding combined polyethers, including following components by weight: 50-60 parts of first kind polyether polyol, 30-40 the second class of part polyether polyol, 5-10 parts of third class polyether polyol, 5-6 parts of auxiliary agents, 12-13 parts of foaming agents and 2-2.5 parts of water；The combined polyether uses the sugar ether of high functionality, sorb alcohol ether and oily ether as first kind polyether polyol, use the high functionality amidogen ether of more number as the second class polyether polyol, reaction system mixing compatibility, crosslinking degree are effectively improved, so that curing be accelerated to solidify；Polyether modified silicon oil is used, with the intersolubility between each component in raising system and with black material, to use amines catalyst, organo-metallic catalyst and catalyst for trimerization as composite catalyst as surfactant, balance foamed time, concertedness improves stripping result.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of fast demoulding combined polyether and its polyurethane with
Preparation method.
Background technique
Hard polyurethane foam combined polyether is one of primary raw material of hard polyurethane foam, also known as white material, black with polymeric MDI nominal
White material.It needs to keep the temperature cold insulation suitable for building heat preservation, cold insulation, solar energy, water heater, freezer, constant heat storage, beer can, refrigeration etc.
Various occasions.
Polyurethane composition polyethers by a variety of polyether polyol (abbreviation monomeric polyether) collocation surfactant, catalyst and
Made of the auxiliary combinations such as foaming agent.It is usually used in all kinds of heat preservations, in the household appliances of refrigeration industry, such as refrigerator, refrigerator etc..Reason
The combined polyether thought should have that rate of closed hole is high, compression strength is good, mechanical performance and good dimension stability and abscess are pure white thin
Greasy feature.
Currently, most domestic produces refrigerator, the combined polyether product demolding time arrived used in the enterprise of refrigerator exists
180-300 seconds, the demand for most reaching 180 seconds fastly, but still being unable to meet production, production efficiency was controlled.
Summary of the invention
For overcome the deficiencies in the prior art, an object of the present invention, which is to provide for one kind, to be reduced demoulding time
To 150 seconds fast demoulding combined polyethers.
The second object of the present invention is to provide the fast demoulding polyurethane comprising the fast demoulding combined polyether.
The third object of the present invention is to provide the preparation method of the fast demoulding polyurethane.
An object of the present invention is implemented with the following technical solutions:
A kind of fast demoulding combined polyether, including following components by weight: 50-60 parts of first kind polyether polyols
Alcohol, 30-40 the second class of part polyether polyol, 5-10 parts of third class polyether polyol, 5-6 parts of auxiliary agents, 12-13 parts of foaming agents and 2-
2.5 parts of water；
The first kind polyether polyol by be 5.5 as initiator degree of functionality using sucrose sugar ether, using sorbierite as starting
The oily ether composition that the sorb alcohol ether and degree of functionality that agent degree of functionality is 6 are 4；
Second class polyether polyol is the amidogen ether for being 4 as initiator degree of functionality using toluenediamine；
Third class polyether polyol is the polyether polyol for being 2 as initiator degree of functionality using diethylene glycol (DEG), propylene glycol；
The auxiliary agent includes polyether modified silicon oil and catalyst.
Further, the catalyst is amines catalyst, organo-metallic catalyst and catalyst for trimerization.
Further, the amines catalyst is cyclohexylamine.
Further, the catalyst for trimerization is TMR-2.
Further, the molecular weight of the sugar ether be 750, degree of functionality 5.5, viscosity 15000mPas.
Further, the molecular weight of the sorb alcohol ether be 700, degree of functionality 6, viscosity 40000mPas.
Further, the molecular weight of the oily ether is 600, degree of functionality 4, viscosity 10000mPas.
Further, the molecular weight of the third class polyether polyol be 1000, viscosity 130mPas, degree of functionality is
2。
Further, including 100 parts by weight such as the described in any item fast demoulding combined polyethers of claim 1-8 and
The black material of 120-130 parts by weight.
The third object of the present invention is realized by following technological means:
A method of preparing above-mentioned fast demoulding polyurethane, which comprises the following steps:
1) first kind polyether polyol, the second class polyether polyol, third class polyether polyol, auxiliary agent of formula ratio are weighed
And water, mixture obtain first material；
2) first material is mixed at 20 DEG C with the foaming agent of formula ratio, obtains combined polyether；
3) combined polyether is mixed with black material by the mass ratio of 1:1.2-1.3, is mixed by high pressure foaming machine, inject mold
In, 40-45 DEG C of temperature control, curing and demolding obtains fast demoulding polyurethane foam.
Compared with prior art, the beneficial effects of the present invention are:
1) by the present invention in that with the high functionality sugar ether, sorb alcohol ether and amidogen ether of increase, while making for oily ether is reduced
Dosage discharges a large amount of heat to reinforce the degree of cross linking in reaction process, and foam is promoted quickly to cure solidification, to improve
The physical property of polyurethane products；
2) present invention is using adding largely using toluenediamine as the amidogen ether of initiator, and each component dissolves each other in enhancing formula
Property, each component and methyl diphenylene diisocyanate mixed effect are promoted, reacts more abundant, thermal discharge is big, accelerates curing
Solidification；
3) present invention is cooperated using amines catalyst and catalyst for trimerization, when active balance expansion rate is with foaming
Between, to mention fast stripping result；
4) the fast demoulding polyurethane that the present invention obtains has preferable physical property, including has preferable heat-insulated guarantor
Warm nature, preferable low temperature anti-contracility, higher compression strength.
Specific embodiment
In the following, being described further in conjunction with specific embodiment to the present invention, it should be noted that is do not collided
Under the premise of, new embodiment can be formed between various embodiments described below or between each technical characteristic in any combination.
The present invention provides a kind of fast demoulding combined polyether, including following components by weight: the 50-60 parts of first kind
Polyether polyol, 30-40 the second class of part polyether polyol, 5-10 parts of third class polyether polyol, 5-6 parts of auxiliary agents, 12-13 parts of hairs
Infusion and 2-2.5 parts of water；
The first kind polyether polyol by be 5.5 sugar ethers using sucrose as the degree of functionality of initiator, using sorbierite as starting
The oily ether composition that the sorb alcohol ether and degree of functionality that the degree of functionality of agent is 6 are 4；
Second class polyether polyol is the amidogen ether for being 500 as initiator, molecular weight using toluenediamine；
Third class polyether polyol is the polyether polyol that molecular weight is 1000, viscosity is 130mPas；
The auxiliary agent includes polyether modified silicon oil and catalyst.
It is adjusted by the dosage of sugar ether, sorb alcohol ether to high functionality, reduces the dosage of oily ether, increases by the second class
The dosage of polyether polyol reinforces the crosslinking degree in reaction process, discharges a large amount of heat, promotes foam quickly to cure solid
Change；In addition use more number using toluenediamine as the amidogen ether of initiator, the intersolubility of each component, makes each in enhancing formula
Component and black material methyl diphenylene diisocyanate mixed effect are promoted, and react more abundant, thermal discharge is big, while adjusting foaming
Time, to realize the effect of fast demoulding.
In following specific embodiments, organo-metallic catalyst is potassium acetate, and amines catalyst is cyclohexylamine.
Embodiment 1
A kind of fast demoulding polyurethane, including fast demoulding combined polyether and black material, wherein fast demoulding combined polyether by
Following components by weight is made: 15 parts of sugar ethers, 15 parts of sorb alcohol ethers, 25 parts of oily ethers, 40 parts of amidogen ethers, 5 parts of low viscosity ethers,
2.5 parts of polyether modified silicon oils, 12.5 parts of foaming agents, 1 part of amines catalyst, 1 portion of organo-metallic catalyst, 1.5 parts of TMR-2 and
2.3 parts of water；Combined polyether and black material are mixed in the ratio of 1:1.25；
The method of preparation method fast demoulding polyurethane, comprising the following steps:
1) it weighs the sugar ether of formula ratio, sorb alcohol ether, oily ether, low viscosity ether, polyether modified silicon oil, amines catalyst, have
Organic metal catalyst, TMR-2 and water, mixture, obtain first material；
2) first material is mixed at 20 DEG C with the foaming agent of formula ratio, obtains combined polyether；
3) combined polyether is mixed with black material by recipe ratio, is mixed by high pressure foaming machine, injected in mold, temperature control 40
DEG C, curing and demolding obtains fast demoulding polyurethane foam.
Embodiment 2
A kind of fast demoulding polyurethane, including fast demoulding combined polyether and black material, wherein fast demoulding combined polyether by
Following components by weight is made: 20 parts of sugar ethers, 20 parts of sorb alcohol ethers, 20 parts of oily ethers, 35 parts of amidogen ethers, 5 parts of low viscosity ethers,
2.5 parts of polyether modified silicon oils, 12 parts of foaming agents, 1 part of amines catalyst, 1 portion of organo-metallic catalyst, 1.5 parts of TMR-2 and 2.3
Part water；Combined polyether and black material are mixed in the ratio of 1:1.25；
The method of preparation method fast demoulding polyurethane, comprising the following steps:
1) it weighs the sugar ether of formula ratio, sorb alcohol ether, oily ether, low viscosity ether, polyether modified silicon oil, amines catalyst, have
Organic metal catalyst, TMR-2 and water, mixture, obtain first material；
2) first material is mixed at 20 DEG C with the foaming agent of formula ratio, obtains combined polyether；
3) combined polyether is mixed with black material by recipe ratio, is mixed by high pressure foaming machine, injected in mold, temperature control 55
DEG C, curing and demolding obtains fast demoulding polyurethane foam.
Embodiment 3:
A kind of fast demoulding polyurethane, including fast demoulding combined polyether and black material, wherein fast demoulding combined polyether by
Following components by weight is made: 25 parts of sugar ethers, 25 parts of sorb alcohol ethers, 15 parts of oily ethers, 30 parts of amidogen ethers, 5 parts of low viscosity ethers,
2.5 parts of polyether modified silicon oils, 12 parts of foaming agents, 1 part of amines catalyst, 1 portion of organo-metallic catalyst, 1.5 parts of TMR-2 and 2.3
Part water；Combined polyether and black material are mixed in the ratio of 1:1.25；
The method of preparation method fast demoulding polyurethane, comprising the following steps:
1) it weighs the sugar ether of formula ratio, sorb alcohol ether, oily ether, low viscosity ether, polyether modified silicon oil, amines catalyst, have
Organic metal catalyst, TMR-2 and water, mixture, obtain first material；
2) first material is mixed at 20 DEG C with the foaming agent of formula ratio, obtains combined polyether；
3) combined polyether is mixed with black material by recipe ratio, is mixed by high pressure foaming machine, injected in mold, temperature control 40
DEG C, curing and demolding obtains fast demoulding polyurethane foam.
In embodiment 1- embodiment 3, used raw material information is as follows:
Sugar ether: the production of polyurethane product company is unified in molecular weight 750, degree of functionality 5.5, viscosity 15000, Jiangsu；
Sorb alcohol ether: the production of polyurethane product company is unified in molecular weight 700, degree of functionality 6, viscosity 40000, Jiangsu；
Oily ether: the production of polyurethane product company is unified in molecular weight 600, degree of functionality 4, viscosity 10000, Jiangsu；
Amidogen ether: the production of polyurethane product company is unified in molecular weight 500, degree of functionality 4, viscosity 20000, Jiangsu；
Low viscosity polyethers: molecular weight 1000, viscosity 130, degree of functionality 2, Dow Chemical's production.
The polyurethane of embodiment 1-3 is 6-8 seconds milky white, wire drawing 50-60 seconds, density is made is 23-24kg/m3Poly- ammonia
Ester.
Comparative example 1:
A kind of polyurethane, including combined polyether and black material, wherein combined polyether is by following components system by weight
At: 10 parts of sugar ethers, 60 parts of oily ethers, 20 parts of amidogen ethers, 10 parts of low viscosity ethers, 2.5 parts of polyether modified silicon oils, 12.5 parts of foaming agents, 2 parts
Amines catalyst, 1.5 parts of TMR-2 and 2.3 part of water；Combined polyether and black material are mixed in the ratio of 1:1.25；
The method of preparation method fast demoulding polyurethane, comprising the following steps:
1) sugar ether, oily ether, low viscosity ether, polyether modified silicon oil, amines catalyst, TMR-2 and the water for weighing formula ratio, are mixed
Match, obtains first material；
2) first material is mixed at 20 DEG C with the foaming agent of formula ratio, obtains combined polyether；
3) combined polyether is mixed with black material by recipe ratio, is mixed by high pressure foaming machine, injected in mold, temperature control 40
DEG C, curing and demolding obtains polyurethane foam.
Comparative example 2:
A kind of polyurethane, including combined polyether and black material, wherein combined polyether is by following components system by weight
At: 10 parts of sugar ethers, 10 parts of sorb alcohol ethers, 50 parts of oily ethers, 20 parts of amidogen ethers, 10 parts of low viscosity ethers, 2.5 parts of polyether modified silicon oils,
12.5 parts of foaming agents, 2 parts of amines catalysts, 1.5 parts of TMR-2 and 2.3 part of water；Combined polyether and black material are mixed in the ratio of 1:1.25
It closes；
The method of preparation method fast demoulding polyurethane, comprising the following steps:
1) weigh the sugar ether of formula ratio, sorb alcohol ether, oily ether, low viscosity ether, polyether modified silicon oil, amines catalyst,
TMR-2 and water, mixture, obtain first material；
2) first material is mixed at 20 DEG C with the foaming agent of formula ratio, obtains combined polyether；
3) combined polyether is mixed with black material by recipe ratio, is mixed by high pressure foaming machine, injected in mold, temperature control 40
DEG C, curing and demolding obtains polyurethane foam.
Comparative example 3:
A kind of polyurethane, including combined polyether and black material, wherein combined polyether is by following components system by weight
At: 15 parts of sugar ethers, 15 parts of sorb alcohol ethers, 40 parts of oily ethers, 20 parts of amidogen ethers, 10 parts of low viscosity ethers, 2.5 parts of polyether modified silicon oils,
12.5 parts of foaming agents, 2 parts of amines catalysts, 1.5 parts of TMR-2 and 2.3 part of water；Combined polyether and black material are mixed in the ratio of 1:1.25
It closes；
The method of preparation method fast demoulding polyurethane, comprising the following steps:
1) weigh the sugar ether of formula ratio, sorb alcohol ether, oily ether, low viscosity ether, polyether modified silicon oil, amines catalyst,
TMR-2 and water, mixture, obtain first material；
2) first material is mixed at 20 DEG C with the foaming agent of formula ratio, obtains combined polyether；
3) combined polyether is mixed with black material by recipe ratio, is mixed by high pressure foaming machine, injected in mold, temperature control 40
DEG C, curing and demolding obtains polyurethane foam.
In comparative example 1- comparative example 3, used raw material information is as follows:
Sugar ether: the production of polyurethane product company is unified in molecular weight 750, degree of functionality 5.5, viscosity 15000, Jiangsu；
Sorb alcohol ether: the production of polyurethane product company is unified in molecular weight 700, degree of functionality 6, viscosity 40000, Jiangsu；
Oily ether: the production of polyurethane product company is unified in molecular weight 600, degree of functionality 4, viscosity 10000, Jiangsu；
Amidogen ether: the production of polyurethane product company is unified in molecular weight 500, degree of functionality 4, viscosity 20000, Jiangsu；
Low viscosity polyethers: molecular weight 1000, degree of functionality 2, viscosity 130, Dow Chemical's production.
The polyurethane of comparative example 1-3 is 6-8 seconds milky white, wire drawing 50-60 seconds, density is made is 23-24kg/m3Poly- ammonia
Ester.
Performance detection and effect assessment
1. demoulding time
The demoulding time of the polyurethane of embodiment 1-3 and comparative example 1-3 is as shown in the table.
1 demoulding time of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Demoulding time s | 150 | 150 | 150 |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Demoulding time s | 270 | 260 | 250 |
The polyurethane of embodiment 1-3 completes demoulding in 150s, and the polyurethane of comparative example 1-3 has demoulding time to be all larger than
250s。
2. physical property
The compressive strength of the polyurethane that embodiment 1-3 and comparative example 1-3 are obtained, thermal coefficient and dimensional stability are as follows
Shown in table.
2 physical property of table
As shown in Table 2, it is strong to be effectively guaranteed compression while accelerating demoulding time for combined polyether provided by the invention
Degree, thermal coefficient, dimensional stability.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. a kind of fast demoulding combined polyether, which is characterized in that including following components by weight: the 50-60 parts of first kind
Polyether polyol, 30-40 the second class of part polyether polyol, 5-10 parts of third class polyether polyol, 5-6 parts of auxiliary agents, 12-13 parts of hairs
Infusion and 2-2.5 parts of water；
The first kind polyether polyol by be 5.5 as initiator degree of functionality using sucrose sugar ether, using sorbierite as initiator official
The oily ether composition that the sorb alcohol ether and degree of functionality that energy degree is 6 are 4；
Second class polyether polyol is the amidogen ether for being 4 as initiator degree of functionality using toluenediamine；
Third class polyether polyol is the polyether polyol for being 2 as initiator degree of functionality using diethylene glycol (DEG), propylene glycol；
The auxiliary agent includes polyether modified silicon oil and catalyst.
2. fast demoulding combined polyether as described in claim 1, which is characterized in that the catalyst is amines catalyst, has
Organic metal catalyst and catalyst for trimerization.
3. fast demoulding combined polyether as claimed in claim 2, which is characterized in that the amines catalyst is cyclohexylamine.
4. fast demoulding combined polyether as claimed in claim 2, which is characterized in that the catalyst for trimerization is TMR-2.
5. fast demoulding combined polyether as described in claim 1, which is characterized in that the molecular weight of the sugar ether is 750, function
Degree is 5.5, viscosity 15000mPas.
6. fast demoulding combined polyether as described in claim 1, which is characterized in that the molecular weight of the sorb alcohol ether be 700,
Degree of functionality is 6, viscosity 40000mPas.
7. fast demoulding combined polyether as described in claim 1, which is characterized in that the molecular weight of the oil ether is 600, function
Degree is 4, viscosity 10000mPas.
8. fast demoulding combined polyether as described in claim 1, which is characterized in that the molecule of the third class polyether polyol
Amount is 1000, viscosity 130mPas, degree of functionality 2.
9. a kind of fast demoulding polyurethane, which is characterized in that including 100 parts by weight as claim 1-8 it is described in any item
The black material of fast demoulding combined polyether and 120-130 parts by weight.
10. a kind of method for preparing fast demoulding polyurethane as claimed in claim 9, which comprises the following steps:
1) weigh the first kind polyether polyol of formula ratio, the second class polyether polyol, third class polyether polyol, auxiliary agent and
Water, mixture, obtains first material；
2) first material is mixed at 20 DEG C with the foaming agent of formula ratio, obtains combined polyether；
3) combined polyether is mixed with black material by the mass ratio of 1:1.2-1.3, is mixed by high pressure foaming machine, injected in mold,
40-45 DEG C of temperature control, curing and demolding obtains fast demoulding polyurethane foam.
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Cited By (2)
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| CN110903457A (en) * | 2019-12-12 | 2020-03-24 | 山东一诺威聚氨酯股份有限公司 | Polyurethane elastomer for manufacturing rapid demoulding high-temperature-resistant transparent model material and preparation method thereof |
| CN112778482A (en) * | 2020-12-30 | 2021-05-11 | 江苏奥斯佳材料科技股份有限公司 | Polyurethane rigid foam composition, polyurethane rigid foam material and preparation method thereof |
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