CN109734860A - A kind of urethane composition for vacuum introducing technology - Google Patents
A kind of urethane composition for vacuum introducing technology Download PDFInfo
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- CN109734860A CN109734860A CN201910021573.5A CN201910021573A CN109734860A CN 109734860 A CN109734860 A CN 109734860A CN 201910021573 A CN201910021573 A CN 201910021573A CN 109734860 A CN109734860 A CN 109734860A
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- diisocyanate
- urethane composition
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- introducing technology
- vacuum introducing
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Abstract
The invention discloses a kind of urethane compositions for vacuum introducing technology, solve the urethane composition of existing low-viscosity, have mechanical strength is low, gel time is short, in air be easy foaming the problems such as.The present invention includes: 1) isocyanate component and 2) reactive component；1) isocyanate component includes: 1a) one or more organic multiple isocyanates；1b) one or more compounds with formula (1) structure；2) reactive component includes: 2a) one or more organic polyhydric alcohols；2b) one or more active deicers.The present invention has very high mechanical strength, good processing performance, while having the effect that foaming is not foamed even less in long gel time and air.
Description
Technical field
The present invention relates to a kind of urethane compositions, and in particular to a kind of polyurethane composition for vacuum introducing technology
Object.
Background technique
The production and selling of China's Polyurethane Industry has accounted for global first place, annual volume of production and marketing millions of tons.But it is most
Polyurethane product is still polyurethane foam (soft bubble or hard bubble), this is mainly due to polyurethane resin intensity is low, operable time
It is short, and be easy to react with water caused by generating bubble.
Vacuum introducing technology be it is a kind of resin is imported in prefabricated composite material mould using vacuum pressure difference, then lead to
The state change of resin is crossed, realizes a kind of technique of composite material preparation.The technique usually requires that resin has lower viscosity,
Long gel time.
There are many companies that polyurethane is used for composite material preparation, but has usually been all made of the technique of pultrusion etc, because
It can receive the disadvantage that polyurethane easily foams and gel time is short for this technique, but also there is limitation simultaneously, ruler can not be prepared
Very little big complex-shaped large-scale composite material.
CN104177581 discloses a kind of urethane composition that can be used for composite material preparation, and the composition storage is steady
It is fixed, but its 25 DEG C of viscositys are higher than 30000mPas, are not used to vacuum introducing technology.CN104045806 discloses a kind of low glutinous
The urethane composition of degree, the composition are made of isocyanate component and polyol component, not can avoid common polyurethane power
Intensity is low, gel time is short, the disadvantages of foaming is easy in air.
Summary of the invention
The technical problems to be solved by the present invention are: the urethane composition of existing low-viscosity, low with mechanical strength,
Gel time is short, the problems such as foaming is easy in air, and the present invention provides the one kind to solve the above problems to import work for vacuum
The urethane composition of skill.
The present invention is achieved through the following technical solutions:
A kind of urethane composition for vacuum introducing technology, comprising: 1) isocyanate component and 2) reactive group
Point；
1) isocyanate component includes:
1a) one or more organic multiple isocyanates；
1b) one or more compounds with formula (1) structure,
Content of the compound of formula (1) structure in isocyanate component is 10%~70%；
2) reactive component includes:
2a) one or more organic polyhydric alcohols；
2b) one or more active deicers.
The present invention makes isocyanates group by the addition of the compound of formula (1) structure by the optimization of isocyanate component
Subpackage contains while having the compound of isocyano and double bond, and the composition for obtaining the present invention finally has very high mechanics strong
Degree, good processing performance, while being not easy to foam, suitable for the preparation of composite material, especially large-scale composite material product
Preparation, performance are very excellent.
Meanwhile by the present invention in that making the present invention in conjunction with the use of active deicer with the compound of such as structural formula (1)
Composition there is long gel time, while avoiding-NCO and react generation carbon dioxide with the water in air and cause to foam.
Thus, the present invention is applied to polyurethane group after cooperating by the compound and active deicer of formula (1) structure
Closing can effectively achieve the effect that mechanical strength is high, gel time is long, foaming is not foamed even less in air in object, and by upper
The mutual cooperation between each component is stated, initial mixing viscosity of the composition at 25 DEG C is smaller, is suitably applied vacuum and leads
Enter in technique.
Further, the R in the formula (1)1Selected from hydrogen, methyl, ethyl or propyl, R2Selected from ethyl, propyl, isopropyl, just
Butyl, tert-butyl or isobutyl group, R3Selected from tolyl, diphenylmethyl alkyl, methylene -3,5,5- trimethylcyclohexyl, six is sub-
Two is sub- between methyl, dicyclohexyl methyl hydride base, cyclohexyl, cyclohexanedimethyleterephthalate, trimethyl -1,6- hexa-methylene, tetramethyl
Aminomethyl phenyl, dimethyl diphenyl, methylcyclohexyl or poly methylene poly phenyl poly isocyanate base.
Further, content of the active deicer in reactive component is 1%~20%；The activity deicer
Include 3- Ethyl-2-Methyl -2- (3- methyl butyl) -1,3- oxazolidine, 3- butyl -2- (1- ethylpentyl) oxazolidine, 2- first
One of base -2- ethyl -3- (2- ethoxy) oxazolidine, triethyl orthoformate, ketimide are a variety of.
Further, 2) reactive component further include:
2c) one or more radical initiators, content of the radical initiator in reactive component are 0.1%
~5%.
Further, the radical initiator includes azodiisobutyronitrile, azobisisoheptonitrile, two isobutyric acid two of azo
One of methyl esters, benzoyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, hydrogen peroxide are a variety of.
In the present invention, the mass ratio of the isocyanate component and reactive component is 20:100~100:20.
The organic multiple isocyanate includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone two
Isocyanates, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, naphthalene diisocyanate, to benzene diisocyanate
Ester, 1,4- cyclohexane diisocyanate, paraphenylene diisocyanate, 1,4- cyclohexane diisocyanate, two isocyanide of phenylenedimethylidyne
Acid esters, cyclohexanedimethyleterephthalate diisocyanate, trimethyl -1,6- hexamethylene diisocyanate, two methylene of tetramethyl isophthalic
Group diisocyanate, dimethyl diphenyl diisocyanate, Methylcyclohexyl diisocyanate, polymethylene multi-phenenyl isocyanate
One of or it is a variety of.
The organic polyhydric alcohol includes polyoxypropyleneglycol, polyether triol, polyether tetrols, polyurea polylol, poly- tetrahydro
Furans glycol, adipate polyester glycol, aromatic polyester polyol, polycaprolactone polyol, polycarbonate glycol, polyacrylic acid
One of ester polyol, polyolefin polyhydric alcohol are a variety of.
By the setting of above-mentioned condition, it can effectively promote initial mixing viscosity of the present composition at 25 DEG C smaller,
Gel time at 23 DEG C is bigger, and then preferably suitable for vacuum introducing technology.Composition is preferably 25 in the present invention
Initial mixing viscosity at DEG C is less than 100mPas, and composition and proportion of the gel time at 23 DEG C greater than 200 minutes make
It is more efficiently suitable for vacuum introducing technology.
Compared with prior art, the present invention having the following advantages and benefits:
1, urethane composition prepared by the present invention does not generate in use or only generates minimal amount bubble, has simultaneously
There are low blending viscosity and long gel time, can be used for the techniques such as vacuum importing, it can be in large-scale composite material product such as wind-powered electricity generation
It is used on blade；
2, urethane composition prepared by the present invention has very high mechanical strength, and it is biggish compound to be used to prepare load
Material product.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment, the present invention is made
Further to be described in detail, exemplary embodiment of the invention and its explanation for explaining only the invention, are not intended as to this
The restriction of invention.
Embodiment 1
A kind of urethane composition for vacuum introducing technology, comprising:
1) isocyanate component
1a) one or more organic multiple isocyanates；
1b) one or more compounds with formula (1) structure,
2) reactive component
2a) one or more organic polyhydric alcohols；
2b) one or more active deicers；
2c) one or more radical initiators.
The specific proportion of the present composition is as shown in table 1.
Table 1
1a in above-mentioned table 1): organic multiple isocyanate is selected as isocyanates PM200；1b): the chemical combination of formula (1) structure
In object, R1 is methyl, and R2 is tert-butyl, R3 dimethylenebenzene between tetramethyl；2a): organic polyhydric alcohol is selected as 40:49's
Polyether polyol MN500 and polyether polyol DL400；2b): active deicer is selected as 3- butyl -2- (1- ethylpentyl) evil
Oxazolidine；2c): radical initiator is selected as initiator MEKP-925H.
The isocyanate component the preparation method comprises the following steps: being added into the compound of formula (1) structure organic more in the present embodiment
Isocyanates is dehydrated under nitrogen protection and is sufficiently mixed uniformly.
The reactive component the preparation method comprises the following steps: organic polyhydric alcohol, active deicer and free radical are drawn in the present embodiment
Agent is sent out proportionally to be uniformly mixed.
Above-mentioned each substance is matched to the composition being combined into the present invention and tests properties by the method for GB/T 31293.
Embodiment 2
The present embodiment and the difference of example 1 in embodiment 1 are that the selection of each substance is different in the present embodiment, specifically set
It sets as shown in table 2.
Table 2
The results are shown in Table 3 after the test unit detection of each embodiment preparation in the present invention.
Table 3
By above-mentioned experimental data: the present invention has low blending viscosity and long gel time, can be used for vacuum
The techniques such as importing, and the present invention has very high mechanical strength, can be used to prepare the biggish composite product of load.
Substance in above-mentioned Tables 1 and 2 is all made of parts by weight metering.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of urethane composition for vacuum introducing technology, comprising: 1) isocyanate component and 2) reactive component,
It is characterized in that；
1) isocyanate component includes:
1a) one or more organic multiple isocyanates；
1b) one or more compounds with formula (1) structure,
Content of the compound of formula (1) structure in isocyanate component is 10%~70%；
2) reactive component includes:
2a) one or more organic polyhydric alcohols；
2b) one or more active deicers.
2. a kind of urethane composition for vacuum introducing technology according to claim 1, which is characterized in that the formula
(1) R in1Selected from hydrogen, methyl, ethyl or propyl, R2Selected from ethyl, propyl, isopropyl, normal-butyl, tert-butyl or isobutyl group,
R3Selected from tolyl, diphenylmethyl alkyl, methylene -3,5,5- trimethylcyclohexyl, hexa-methylene, dicyclohexyl methyl hydride base,
Dimethylenebenzene between cyclohexyl, cyclohexanedimethyleterephthalate, trimethyl -1,6- hexa-methylene, tetramethyl, dimethyl diphenyl,
Methylcyclohexyl or poly methylene poly phenyl poly isocyanate base.
3. a kind of urethane composition for vacuum introducing technology according to claim 1, which is characterized in that the work
Property content of the deicer in reactive component be 1%~20%；The activity deicer includes 3- Ethyl-2-Methyl -2- (3-
Methyl butyl) -1,3- oxazolidine, 3- butyl -2- (1- ethylpentyl) oxazolidine, 2- methyl -2- ethyl -3- (2- ethoxy) evil
One of oxazolidine, triethyl orthoformate, ketimide are a variety of.
4. a kind of urethane composition for vacuum introducing technology according to claim 1, which is characterized in that it is described 2)
Reactive component further include:
2c) one or more radical initiators, content of the radical initiator in reactive component be 0.1%~
5%.
5. a kind of urethane composition for vacuum introducing technology according to claim 4, which is characterized in that it is described from
It include azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, benzoyl peroxide, peroxide by base initiator
Change one of the benzoyl tert-butyl ester, methyl ethyl ketone peroxide, hydrogen peroxide or a variety of.
6. a kind of urethane composition for vacuum introducing technology according to claim 1, which is characterized in that described different
Isocyanate component and the mass ratio of reactive component are 20:100~100:20.
7. a kind of urethane composition for vacuum introducing technology according to claim 1, which is characterized in that described to have
Machine polyisocyanates includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate, six methylenes
Group diisocyanate, dicyclohexyl methyl hydride diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, 1,4- hexamethylene two
Isocyanates, paraphenylene diisocyanate, 1,4- cyclohexane diisocyanate, benzene dimethylene diisocyanate, hexamethylene two are sub-
Methyl diisocyanate, trimethyl -1,6- hexamethylene diisocyanate, tetramethyl m-xylylene diisocyanate, two
One of methyl biphenyl diisocyanate, Methylcyclohexyl diisocyanate, polymethylene multi-phenenyl isocyanate are a variety of.
8. a kind of urethane composition for vacuum introducing technology according to claim 1, which is characterized in that described to have
Machine polyalcohol includes polyoxypropyleneglycol, polyether triol, polyether tetrols, polyurea polylol, polytetrahydrofuran diol, adipic acid
Polyester-diol, aromatic polyester polyol, polycaprolactone polyol, polycarbonate glycol, polyacrylate polyol, polyolefin
One of polyalcohol is a variety of.
9. a kind of urethane composition for vacuum introducing technology according to claim 1, which is characterized in that the combination
Initial mixing viscosity of the object at 25 DEG C is less than 100mPas.
10. a kind of urethane composition for vacuum introducing technology according to claim 1, which is characterized in that the group
Gel time of the object at 23 DEG C is closed to be greater than 200 minutes.
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| CN113501930A (en) * | 2021-06-23 | 2021-10-15 | 四川东树新材料有限公司 | Cast polyurethane resin for wind power blade and preparation method thereof |
| CN114230746A (en) * | 2022-01-14 | 2022-03-25 | 万华化学集团股份有限公司 | Free radical polymerizable polyurethane composition, preparation method and application thereof |
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| CN111349206A (en) * | 2020-04-14 | 2020-06-30 | 万华节能科技(烟台)有限公司 | High-strength polyurethane heat-insulation cushion block bi-component raw material for refrigeration house and preparation method thereof |
| CN111349206B (en) * | 2020-04-14 | 2022-02-08 | 万华节能科技(烟台)有限公司 | High-strength polyurethane heat-insulation cushion block bi-component raw material for refrigeration house and preparation method thereof |
| CN113501930A (en) * | 2021-06-23 | 2021-10-15 | 四川东树新材料有限公司 | Cast polyurethane resin for wind power blade and preparation method thereof |
| CN113501930B (en) * | 2021-06-23 | 2022-04-01 | 四川东树新材料有限公司 | Cast polyurethane resin for wind power blade and preparation method thereof |
| CN114230746A (en) * | 2022-01-14 | 2022-03-25 | 万华化学集团股份有限公司 | Free radical polymerizable polyurethane composition, preparation method and application thereof |
| CN114230746B (en) * | 2022-01-14 | 2023-12-19 | 万华化学集团股份有限公司 | Polyurethane composition capable of free radical polymerization, preparation method and application thereof |
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