CN110283325A - A kind of preparation method for the organic silicon surfactant being used to prepare hard polyurethane foam - Google Patents
A kind of preparation method for the organic silicon surfactant being used to prepare hard polyurethane foam Download PDFInfo
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- CN110283325A CN110283325A CN201910585414.8A CN201910585414A CN110283325A CN 110283325 A CN110283325 A CN 110283325A CN 201910585414 A CN201910585414 A CN 201910585414A CN 110283325 A CN110283325 A CN 110283325A
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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Abstract
The present invention provides a kind of preparation methods of organic silicon surfactant for being used to prepare hard polyurethane foam, including reacting as the monohydroxy polyethers of initiator with allyl chloride or methallyl chloride using monohydric alcohol or alkyl alcohol ether, allyl polyethenoxy ether or polyoxyethylene ether are obtained；Weigh according to parts by weight allyl polyethenoxy ether perhaps polyoxyethylene ether, low the hydrogen containing siloxane allyl polyethenoxy ether or polyoxyethylene ether, low hydrogen containing siloxane weight ratio be 300 ~ 400:100 ~ 200；Allyl polyethenoxy ether or polyoxyethylene ether are first added in a vessel, then low hydrogen containing siloxane is added, stirs, is heated to 75 ~ 85 DEG C, catalyst is added, copolyreaction obtains silicone copolymer surfactants.The present invention is mixed with water may be implemented self-emulsifying, appearance transparent；And organic silicon surfactant of the invention can improve the epidermis of hard foamed poly urethane.
Description
Technical field
The invention belongs to chemical fields, are related to a kind of surfactant, specifically one kind is used to prepare rigid polyurethane
The preparation method of the organic silicon surfactant of matter foam.
Background technique
The existing organic silicon surfactant for being used to prepare hard polyurethane foam is all using containing hydrogen silicone oil and allyl
Alcohol is as initiator, and the allyl polyether reaction of ethylene oxide and propylene oxide alkylated reaction is prepared, commonly used in system
The allyl polyether of the organic silicon surfactant of standby hard polyurethane foam is not end capped polyether.
Although higher using acetyl blocked allyl polyether ending ratio, portioned product can achieve 98% sealing end
Rate, but the organic silicon surfactant of this kind of allyl polyether preparation mixes with water and amines catalyst and will appear milky white shape,
It is opaque, it can go bad after mixing immediately, influence the preparation of hard polyurethane foam.
95%, and alkyl-blocked organosilicon table are generally smaller than using the ending ratio of alkyl-blocked allyl polyether
The poor compatibility of face activating agent and polyurethane combined material.
Summary of the invention
The purpose of the present invention is to provide a kind of systems of organic silicon surfactant for being used to prepare hard polyurethane foam
Preparation Method, the preparation method of this organic silicon surfactant for being used to prepare hard polyurethane foam will solve existing
Organic silicon surfactant in technology is mixed with water and amines catalyst will appear milky white shape, opaque, immediately after mixing
The technical issues of rotten technical problem can occur, while to solve the poor compatibility with polyurethane combined material.
The present invention provides a kind of preparation method of organic silicon surfactant for being used to prepare hard polyurethane foam, packets
Include following steps:
1) the monohydroxy polyethers and allyl chloride or methallyl chloride using monohydric alcohol or alkyl alcohol ether as initiator
Reaction, obtains allyl polyethenoxy ether or polyoxyethylene ether；In the allyl polyethenoxy ether or polyoxyethylene
In ether, the molar percentage of ethylene oxide group and propylene oxide group is 40~50%:50~60%；
2) allyl polyethenoxy ether or polyoxyethylene ether, low hydrogen containing siloxane are weighed according to parts by weight, it is described
The hydrogen content of low hydrogen containing siloxane be 0.1~0.2%, it is the allyl polyethenoxy ether or polyoxyethylene ether, low
The weight ratio of hydrogen containing siloxane is 300~400:100~200；
3) allyl polyethenoxy ether or polyoxyethylene ether are first added in a vessel, then by low hydrogeneous poly- silicon oxygen
Alkane is added, and starts to stir, and is heated to 75~85 DEG C, and catalyst chloroplatinic acid ethanol solution is added and obtains after copolyreaction 2~4 hours
To as clear as crystal weak yellow liquid, as silicone copolymer surfactants.
Further, the monohydric alcohol or alkyl alcohol ether are butanol butyl ether or butyl glycol ether or glycol propyl ether
Or any one in triethylene glycol methyl ether.
Specifically, hydrogen content refers to mass percent of the hydrogen in low hydrogen containing siloxane.
Further, in step 2), after chloroplatinic acid ethanol solution is added, so that chloroplatinic acid is dense in entire reaction system
Degree is 15ppm.
Further, remaining allyl chloride or methallyl chloride are deviate from using vacuum in step 1).
Monohydroxy polyethers and allyl chloride or methallyl of the present invention using monohydric alcohol or alkyl alcohol ether as initiator
The reaction preparation of base chlorine, prepares the allyl polyether of 100% sealing end, then anti-with the allyl polyether and low hydrogen containing siloxane
Organic silicon surfactant should be prepared, prepared by the present invention is a kind of the organic of the not hydroxyl for hard polyurethane foam
Silicon surface active agent.Such organic silicon surfactant can improve the epidermis cavity of hard polyurethane foam, increase foams
Mobility.
The present invention is compared with prior art, its technical effect is that actively and apparent.It is complete that the present invention can prepare 100%
The organic silicon surfactant of ending ratio；Organic silicon surfactant of the invention simultaneously is mixed with water may be implemented self-emulsifying,
Appearance transparent；And organic silicon surfactant of the invention can improve the epidermis of hard foamed poly urethane.
Detailed description of the invention
Fig. 1 shows that the blibbing of the present invention and control group compares.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products of commercially available acquisition can be passed through.
The preparation of 1 silicone copolymer surfactants of embodiment
There are four mouthfuls of burnings of fixed device, temperature incubation function, mechanical stirring, thermocouple and the 500ml for being connected with nitrogen at one
In bottle, the allyl polyethenoxy ether that the average molecular weight of the allyl chloride sealing end of 350g butanol starting is 2100 is added, this is poly-
Ethylene oxide ether contains the propylene oxide base that the ethylene oxide group that molar percentage is 45% and molar percentage are 55%, then
The low hydrogen containing siloxane of 150g (hydrogen content 0.15%) is added in four-hole boiling flask, starts to stir, extremely using heating mantle heats
It 80 DEG C, stirs 5 minutes, chloroplatinic acid ethanol solution is added, after chloroplatinic acid ethanol solution is added, so that chloroplatinic acid is in entire reactant
Concentration in system is 15ppm.After reaction 3 hours, as clear as crystal weak yellow liquid is obtained, as Organosiliconcopolymere surface is living
Property agent, referring to GB/T 7383-2007 test hydroxyl value be 0.
The preparation of 2 silicone copolymer surfactants of embodiment
There are four mouthfuls of burnings of fixed device, temperature incubation function, mechanical stirring, thermocouple and the 500ml for being connected with nitrogen at one
In bottle, the polyoxyethylene ether that the average molecular weight of the allyl chloride sealing end of 350g butyl glycol ether starting is 2200, polyoxy is added
Vinethene contains the propylene oxide base that the ethylene oxide group that molar percentage is 45% and molar percentage are 55%, then will
The low hydrogen containing siloxane of 150g (hydrogen content 0.15%) is added in four-hole boiling flask, starts to stir, using heating mantle heats to 80
DEG C, it stirs 5 minutes, chloroplatinic acid ethanol solution is added, after chloroplatinic acid ethanol solution is added, so that chloroplatinic acid is in entire reaction system
In concentration be 15ppm.After reaction 3 hours, as clear as crystal weak yellow liquid, as Organosiliconcopolymere surface-active are obtained
Agent, testing hydroxyl value referring to GB/T 7383-2007 is 0.
The preparation of 3 silicone copolymer surfactants of embodiment
There are four mouthfuls of burnings of fixed device, temperature incubation function, mechanical stirring, thermocouple and the 500ml for being connected with nitrogen at one
In bottle, the polyoxyethylene ether that the average molecular weight of the allyl chloride sealing end of 350g glycol propyl ether starting is 2300, polyoxy is added
Vinethene contains the propylene oxide base that the ethylene oxide group that molar percentage is 45% and molar percentage are 55%, then will
The low hydrogen containing siloxane of 150g (hydrogen content 0.15%) is added in four-hole boiling flask, starts to stir, using heating mantle heats to 80
DEG C, it stirs 5 minutes, chloroplatinic acid ethanol solution is added, after chloroplatinic acid ethanol solution is added, so that chloroplatinic acid is in entire reaction system
In concentration be 15ppm.After reaction 3 hours, as clear as crystal weak yellow liquid, as Organosiliconcopolymere surface-active are obtained
It is 0 that agent, which tests hydroxyl value referring to GB/T 7383-2007,.
The preparation of 4 silicone copolymer surfactants of embodiment
There are four mouthfuls of burnings of fixed device, temperature incubation function, mechanical stirring, thermocouple and the 500ml for being connected with nitrogen at one
In bottle, the polyoxyethylene that the average molecular weight of the methallyl chloride sealing end of 350g triethylene glycol methyl ether starting is 1900 is added
Ether, polyoxyethylene ether contain the propylene oxide that the ethylene oxide group that molar percentage is 40% and molar percentage are 60%
The low hydrogen containing siloxane of 150g (hydrogen content 0.15%) is then added in four-hole boiling flask, starts to stir, using heating mantle by base
80 DEG C are heated to, is stirred 5 minutes, chloroplatinic acid ethanol solution is added, after chloroplatinic acid ethanol solution is added, so that chloroplatinic acid is entire
Concentration in reaction system is 15ppm.After reaction 3 hours, as clear as crystal weak yellow liquid, as Organosiliconcopolymere are obtained
Surfactant, testing hydroxyl value referring to GB/T 7383-2007 is 0.
Test example 1
Silicone copolymer surfactants prepared by embodiment 1-4 are prepared into hard polyurethane foam as group 1-4；
Selecting commercially available organosilicon L-6900 and B-8545 simultaneously, 1-2 is prepared for hard polyurethane foam, original used as a control group
Material is as shown in table 1
Table 1 prepares hard polyurethane foam
Wherein, PIR plate combined polyether contains polyether polyol, polyester polyol, catalyst, water, fire retardant and physics
Foaming agent；Its viscosity is 400-600mPa.s, hydroxyl value 200-300mgKOH/g, water content 1.5-2.5%, physical blowing agent
Content is 10-20%；
PIR plate combined polyether includes the ingredient of following mass fractions: 4 parts of polyether polyol NJ6207, polyester polyol
6 parts of PS-2412,4.0 parts of catalyst, H22.0 parts of O, 15 parts of fire retardant TCPP, 15 parts of physical blowing agent pentane.
According to above-mentioned formula, each ingredient is added in stainless steel mixing kettle, it is small with 500 revs/min of revolving speed stirring 1 at room temperature
When, blowing is up to combined polyether.
NJ6207 is bought from Jurong Ningwu new material Co., Ltd.
PS-2412 is bought from Si Taipan (Nanjing) Chemical Co., Ltd..
TCPP is bought from Jiangsu Yoke Chemical Co., Ltd..
Catalyst is bought from Ying Chuan Specialty Chemical (Shanghai) Co., Ltd..
PM200 is polymeric MDI, is bought from Yantai Wanhua.
L-6900 is bought from U.S.'s Mitugao New Material Group.
B-8545 is bought from Ying Chuan Specialty Chemical (Shanghai) Co., Ltd..
Upper table statistics indicate that, it is compared with the control group, hard made from silicone copolymer surfactants provided by the invention
Matter polyurethane foam has the air blister defect that can not only improve foam surface, can also improve mobile performance, the bubble of material system
The compression strength of foam and the dimensional stability of foam.
2 test method of table
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (4)
1. a kind of preparation method for the organic silicon surfactant for being used to prepare hard polyurethane foam, it is characterised in that: including
Following steps:
1) it is reacted as the monohydroxy polyethers of initiator with allyl chloride or methallyl chloride using monohydric alcohol or alkyl alcohol ether,
Obtain allyl polyethenoxy ether or polyoxyethylene ether；In the allyl polyethenoxy ether or polyoxyethylene ether,
The molar percentage of ethylene oxide group and propylene oxide group is 40~50%:50~60%；
2) allyl polyethenoxy ether or polyoxyethylene ether, low hydrogen containing siloxane are weighed according to parts by weight, and described is low
The hydrogen content of hydrogen containing siloxane is 0.1~0.2%, the allyl polyethenoxy ether or polyoxyethylene ether, low hydrogeneous
The weight ratio of polysiloxanes is 300~400:100~200；
3) allyl polyethenoxy ether or polyoxyethylene ether are first added in a vessel, then adds low hydrogen containing siloxane
Enter, start to stir, be heated to 75~85 DEG C, catalyst chloroplatinic acid ethanol solution is added, after copolyreaction 2~4 hours, obtains clear
Clear transparent weak yellow liquid, as silicone copolymer surfactants.
2. the preparation method of the organic silicon surfactant according to claim 1 for being used to prepare hard polyurethane foam,
It is characterized by: the monohydric alcohol or alkyl alcohol ether are butanol butyl ether or butyl glycol ether or glycol propyl ether or three
Any one in ethylene glycol monomethyl ether.
3. the preparation method of the organic silicon surfactant according to claim 1 for being used to prepare hard polyurethane foam,
It is characterized by: in step 2), after chloroplatinic acid ethanol solution is added, so that concentration of the chloroplatinic acid in entire reaction system is
15ppm。
4. the preparation method of the organic silicon surfactant according to claim 1 for being used to prepare hard polyurethane foam,
It is characterized by: remaining allyl chloride or methallyl chloride are deviate from using vacuum in step 1).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910585414.8A CN110283325A (en) | 2019-07-01 | 2019-07-01 | A kind of preparation method for the organic silicon surfactant being used to prepare hard polyurethane foam |
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| CN201910585414.8A CN110283325A (en) | 2019-07-01 | 2019-07-01 | A kind of preparation method for the organic silicon surfactant being used to prepare hard polyurethane foam |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929959A (en) * | 2021-11-25 | 2022-01-14 | 南京美思德新材料有限公司 | Foam surfactant, preparation method thereof and foam |
| CN115433336A (en) * | 2022-07-14 | 2022-12-06 | 苏州思德新材料科技有限公司 | Preparation method of novel polyurethane surfactant |
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| CN101982481A (en) * | 2010-10-08 | 2011-03-02 | 广东标美硅氟新材料有限公司 | Preparation method of alkyl blocked allyl polyether |
| CN102050945A (en) * | 2010-12-13 | 2011-05-11 | 上海东大聚氨酯有限公司 | Polyether glycol, polyurethane rigid foamed plastic and preparation methods thereof |
| CN106750327A (en) * | 2016-12-29 | 2017-05-31 | 中国石油天然气股份有限公司 | A kind of modified polyether and its preparation method and application |
| WO2017161162A1 (en) * | 2016-03-18 | 2017-09-21 | Tyco Fire Products Lp | Organosiloxane compounds as active ingredients in fluorine free fire suppression foams |
| CN109851835A (en) * | 2018-12-20 | 2019-06-07 | 南京美思德新材料有限公司 | Hard polyurethane foams organic silicon surfactant and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101982481A (en) * | 2010-10-08 | 2011-03-02 | 广东标美硅氟新材料有限公司 | Preparation method of alkyl blocked allyl polyether |
| CN102050945A (en) * | 2010-12-13 | 2011-05-11 | 上海东大聚氨酯有限公司 | Polyether glycol, polyurethane rigid foamed plastic and preparation methods thereof |
| WO2017161162A1 (en) * | 2016-03-18 | 2017-09-21 | Tyco Fire Products Lp | Organosiloxane compounds as active ingredients in fluorine free fire suppression foams |
| CN106750327A (en) * | 2016-12-29 | 2017-05-31 | 中国石油天然气股份有限公司 | A kind of modified polyether and its preparation method and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929959A (en) * | 2021-11-25 | 2022-01-14 | 南京美思德新材料有限公司 | Foam surfactant, preparation method thereof and foam |
| CN113929959B (en) * | 2021-11-25 | 2022-11-22 | 南京美思德新材料有限公司 | Foam surfactant, preparation method thereof and foam |
| CN115433336A (en) * | 2022-07-14 | 2022-12-06 | 苏州思德新材料科技有限公司 | Preparation method of novel polyurethane surfactant |
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Address after: 201507 Shanghai city Jinshan District Caojing town industry Road No. 52 Applicant after: Shanghai Mahou New Material Technology Co.,Ltd. Address before: 201507 Shanghai city Jinshan District Caojing town industry Road No. 52 Applicant before: SHANGHAI MAIPU NEW MATERIAL TECHNOLOGY Co.,Ltd. |
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Application publication date: 20190927 |