CN110041553A - A kind of foam stabiliser can be used for full water foamed system - Google Patents
A kind of foam stabiliser can be used for full water foamed system Download PDFInfo
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- CN110041553A CN110041553A CN201910400650.8A CN201910400650A CN110041553A CN 110041553 A CN110041553 A CN 110041553A CN 201910400650 A CN201910400650 A CN 201910400650A CN 110041553 A CN110041553 A CN 110041553A
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- full water
- foam stabiliser
- polyether
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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
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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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- 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
- C08J9/0014—Use of organic additives
- C08J9/0042—Use of organic additives containing silicon
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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
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to polyurethane foam stabilization techniques, and in particular to a kind of foam stabiliser that can be used for full water foamed system.The foam stabiliser is modified polyether grafted-organosilicon surfactant；The body material for preparing of the modified polyether grafted-organosilicon surfactant includes silicon oil of low hydrogen content and unsaturated polyether, and weight ratio is 1:(1~10).
Description
Technical field
The present invention relates to polyurethane foam stabilization techniques, and in particular to steady to a kind of foam that can be used for full water foamed system
Determine agent.
Background technique
Polyurethane foam plastics is one of principal item of polyurethane synthetic material, small with porosity, relative density
The advantages that high with specific strength.Soft, semi-rigid and hard polyurethane foams modeling can be made by adjusting the raw material and formula used
Material etc..Polyurethane foam plastics application range is very extensive, almost penetrates into each department of national economy, be widely used in furniture,
The industries such as bed accessory, transport, refrigeration, building, insulation become one of indispensable material.
Foam stabiliser is one of the key component in polyurethane foam plastics factory formula, in polyurethane foam plastics
Effect played in production process is such as emulsified, is nucleated, foam is stable and the mobility of material mutually restricts.For example, working as
When the surface tension of polyurethane foam system is reduced many by foam stabiliser, the emulsification of material and mobility can be improved, but this
But there is negative effect to nucleation and foam stabilization.Therefore, the molecular structure for how designing foam stabiliser reaches its various performance
It is the key that guarantee the foam stabiliser quality to overall balance.Meanwhile when pursuing raising foam stabiliser performance, how
Optimize its production technology as far as possible to reduce the discharge of environmentally harmful pollutant and reduce product cost and foam stabiliser
The significant challenge that practitioner faces.Instantly, traditional foaming agent F-11 is disabled comprehensively, and 141B limitation uses, Quan Shuifa
Foam system is most promising one of application.Developing the novel foam stabiliser for full aqueous systems seems very urgent.
Summary of the invention
In view of the above technical problems, it is steady to provide a kind of foam that can be used for full water foamed system for the first aspect of the present invention
Determine agent, the foam stabiliser is modified polyether grafted-organosilicon surfactant；Modified polyether grafted-organosilicon surface
The body material for preparing of activating agent includes silicon oil of low hydrogen content and unsaturated polyether, and weight ratio is 1:(1~10).
As a kind of perferred technical scheme, the hydrogen content of the silicon oil of low hydrogen content is 0.05~0.8wt%.
As a kind of perferred technical scheme, the silicon oil of low hydrogen content prepare raw material include octamethylcy-clotetrasiloxane,
Hexamethyldisiloxane and high containing hydrogen silicone oil.
As a kind of perferred technical scheme, the preparation method of the modified polyether grafted-organosilicon surfactant includes
Following steps:
1) silicon oil of low hydrogen content, unsaturated polyether, dispersing agent and complex metal catalyst are added in reaction kettle, in reaction temperature
Degree is 80-120 DEG C, under normal pressure, reacts 2-8 hours, obtains intermediate product；
2) sulfonation processing and/or phosphatizing treatment are carried out to obtain the final product to the intermediate product in the 1) step.
As a kind of perferred technical scheme, the unsaturated polyether is allyl alcohol polyether and/or allyl polyethenoxy
Polyoxypropylene epoxy group ether.
As a kind of perferred technical scheme, the sulfonation processing includes the following steps:
Potassium bisulfite and the intermediate product are dissolved in the mixed solution of isopropyl alcohol and water, and at 70~80 DEG C
Reaction 2~6 hours, discharges to obtain the final product；The volume ratio of the isopropanol and water is (2~10): 1.
As a kind of perferred technical scheme, the weight ratio of the potassium bisulfite and intermediate product is 1:
(5~60).
As a kind of perferred technical scheme, the phosphatizing treatment includes the following steps:
The intermediate product and phosphoric acid are added in reaction kettle, the first of 50~60wt% of monomer gross mass is then added
Benzene dissolution, and under conditions of being passed through nitrogen, 90~100 DEG C insulation reaction 3~5 hours, then handle to obtain the final product.
As a kind of perferred technical scheme, the weight ratio of the intermediate product and phosphoric acid is (8~30): 1.
The second aspect of the invention provides a kind of hard polyurethane foam material, prepares raw material, in parts by weight,
Including following component:
Full water combined polyether 100
Isocyanates 125~150
Stabilizer 1.5~3；
The stabilizer is the foam stabiliser that can be used for full water foamed system as described above.
Specific embodiment
It is further clear, complete that the technical characteristic work in technical solution is provided to the present invention With reference to embodiment
Description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, every other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, shall fall within the protection scope of the present invention.
Word " preferred ", " preferably ", " preferred " in the present invention etc. refer to, can provide certain in some cases
The embodiment of the present invention of a little beneficial effects.However, other embodiments may also under identical circumstances or in the case of other
It is preferred.In addition, not implying that other embodiments are unavailable to the statement of one or more preferred embodiments, it is not yet
It is intended to exclude other embodiments except the scope of the present invention.
It should be appreciated that expression for example illustrates in the case where in addition in any operational instances or otherwise pointing out
All numbers of the amount of ingredient used in book and claim should be understood to be modified by term " about " in all cases.
In view of the above technical problems, it is steady to provide a kind of foam that can be used for full water foamed system for the first aspect of the present invention
Determine agent, the foam stabiliser is modified polyether grafted-organosilicon surfactant；Modified polyether grafted-organosilicon surface
The body material for preparing of activating agent includes silicon oil of low hydrogen content and unsaturated polyether, and weight ratio is 1:(1~10).
Silicon oil of low hydrogen content (PMHS) in the present invention, which refers to, contains portion on the end of organosilicon macromolecule main chain or side chain
Point or each chain link contain the reactive hydrogen atom that may participate in cross-linking reaction, these reactive hydrogen atoms can with contain unsaturated double-bond
Or three monomer, oligomer or the polymer of key occur hydrosilylation under Pt catalyst action, form grafting, block or net
The copolymer of shape.
In some embodiments, the hydrogen content of the silicon oil of low hydrogen content is 0.05~0.8wt%.
The hydrogen content of heretofore described silicon oil of low hydrogen content can be by titration measuring, specifically can be according to following behaviour
It carries out: preparing the acetic acid solution 0.2mol/L of bromine first, then prepare 10% liquor kalii iodide, then prepare 0.1mol/L
Hypo solution.The concentration for having demarcated sodium thiosulfate, is demarcated with potassium bichromate, finally samples containing hydrogen silicone oil 0.07g,
In the iodine flask of 250ml, add 20ml carbon tetrachloride, add the acetic acid solution of 10 milliliters of bromines, after standing 2 hours, adds 25 milliliters
Potassium iodide is titrated to terminal with the sodium thiosulfate sodium just demarcated, can calculate hydrogen content.
Heretofore described silicon oil of low hydrogen content can be obtained from purchase on the market, can also be obtained by self-control
In some embodiments, the raw material for preparing of the silicon oil of low hydrogen content includes octamethylcy-clotetrasiloxane, hexamethyl
Disiloxane and high containing hydrogen silicone oil.
Preferably, the octamethylcy-clotetrasiloxane, hexamethyldisiloxane and high containing hydrogen silicone oil charged material weight ratio are
(20~1000): (1~32): (6~50).
Preferably, the preparation method of the silicon oil of low hydrogen content includes the following steps:
By octamethylcy-clotetrasiloxane, hexamethyldisiloxane and high containing hydrogen silicone oil under acidic catalyst effect, in 30-
It is reacted 4-12 hours at 80 DEG C, obtains the silicon oil of low hydrogen content that hydrogen content is 0.05-0.8%.
The quality of the acidic catalyst is octamethylcy-clotetrasiloxane, hexamethyldisiloxane and high containing hydrogen silicone oil three
The 0.5%-6% of quality sum, using strong resin or Emathlite.
In some embodiments, the preparation method of the modified polyether grafted-organosilicon surfactant includes following step
It is rapid:
1) silicon oil of low hydrogen content, unsaturated polyether, dispersing agent and complex metal catalyst are added in reaction kettle, in reaction temperature
Degree is 80-120 DEG C, under normal pressure, reacts 2-8 hours, obtains intermediate product；
2) sulfonation processing and/or phosphatizing treatment are carried out to obtain the final product to the intermediate product in the 1) step.
Complex metal catalyst in the present invention can select any can make between carbon-to-carbon unsaturated double-bond and Si -- H bond
Catalyst of Michael addition reaction, such as platinum rhodium complex, chloroplatinic acid etc. can occur.
The effect of heretofore described dispersing agent mainly has the ingredients such as silicon oil of low hydrogen content, unsaturated polyether, catalyst
Effect dispersion, improves reaction conversion ratio, reduces side reaction generation etc..The dispersing agent can be small-molecular-weight polyethers, and small molecule is more
First alcohol etc., such as diethylene glycol (DEG), triethylene glycol etc..
In some embodiments, the unsaturated polyether is allyl alcohol polyether and/or allyl polyethenoxy polyoxy third
Alkene epoxy group ether.
Preferably, the unsaturated polyether be allyl alcohol polyether and allyl polyethenoxy polyoxypropylene epoxy group ether,
Weight ratio is 2:1.
It is further preferred that the hydroxyl value (mgKOH/g) of the allyl alcohol polyether is 30~130, Zhejiang Real Madrid section can be selected
Products such as HMS-229R, HMS-232R, HMS-235R of skill limited liability company etc..The allyl polyethenoxy polyoxypropylene
The weight average molecular weight of epoxy group ether is 500~600, is purchased from the HY series of products of Historic Area of Zhongshan in Nanjing City Chemical Co., Ltd., molecular weight
It is 300~1200.
In some embodiments, the sulfonation processing includes the following steps:
Potassium bisulfite and the intermediate product are dissolved in the mixed solution of isopropyl alcohol and water, and at 70~80 DEG C
Reaction 2~6 hours, discharges to obtain the final product；The volume ratio of the isopropanol and water is (2~10): 1.
In some embodiments, the weight ratio of the potassium bisulfite and intermediate product is 1:(5~60).
In some embodiments, the phosphatizing treatment includes the following steps:
The intermediate product and phosphoric acid are added in reaction kettle, the first of 50~60wt% of monomer gross mass is then added
Benzene dissolution, and under conditions of being passed through nitrogen, 90~100 DEG C insulation reaction 3~5 hours, then handle to obtain the final product.
In some embodiments, the weight ratio of the intermediate product and phosphoric acid is (8~30): 1.
By carrying out sulfonation or Phosphation processing to polyether graft modified organic silicone oil in the present invention, foam can be made
Stabilizer has multi-functional.Due to the introducing of sulphonic acid ester or bound phosphate groups, the hydrophily of polyether grafting organic silicone oil is improved,
The solvation between organic silicone oil and moisture value is improved, so as to improve foam stabiliser to the stability of foam.In addition,
Since the introducing of bound phosphate groups is so that foamed material is in burning, the phosphate ester element in foam stabiliser, which decomposes, generates phosphoric acid
Non-ignitibility liquid film, boiling point is up to 300 DEG C.Meanwhile phosphoric acid is further dehydrated and generates metaphosphoric acid, metaphosphoric acid further gathers
Symphysis is at poly-metaphosphoric acid.In this process, blanketing effect is not only played by the coating that phosphoric acid generates, but also due to generation
Poly-metaphosphoric acid is strong acid, is very strong dehydrating agent, so that polymer is dehydrated and is carbonized, changes the mode of polymer combustion process simultaneously
Carbon film is formed on its surface to completely cut off air, to also play stronger resistance while improving the effect of stabilizer stable foam
Fuel efficiency fruit.
The second aspect of the invention provides a kind of hard polyurethane foam material, prepares raw material, in parts by weight,
Including following component:
Full water combined polyether 100
Isocyanates 125~150
Stabilizer 1.5~3；
The stabilizer is the foam stabiliser that can be used for full water foamed system as described above.
Combined polyether in the present invention includes 1~8wt% of polyether polyol, 2.0~5.0wt% of catalyst and water, wherein
Percentage be each ingredient based on ratio shared by combined polyether gross mass.
The concrete type of the full water polyether polyol combination material is not particularly limited in the present invention, can use in mountain
Full water combined polyether BT-328W, full water combined polyether B607, the full water combined polyether B705 of the Science and Technology Ltd. of the primary scholar in city
Deng.
The concrete type of the polyether polyol is not particularly limited in the present invention, Hebei Yadong chemical industry collection can be used
YD-380, YD-450BC, YD-480, YD-889, YD-1050, YD-4110, YD-4114, YD-8238 etc. of Co., Ltd, group.
The catalyst is amines catalyst.The amines catalyst can select bis- (dimethylaminoethyl) ethers,
Five methyl diethylentriamine, dimethyl cyclohexyl amine, triethylene diamine, 1,3,5- tri- (dimethylamino-propyl)-Hexahydrotriazine and
N, N- dimethyl benzylamine etc..It further include sodium soap/potassium (soap base, including sodium laurate/potassium, Sodium myristate/potassium, palmitinic acid
Sodium/potassium, odium stearate/potassium) etc..
The chemical foaming agent can be water.
There is no special restrictions for the isocyanates in the present invention, if meet isocyanate groups index 90~
Between 120.The isocyanates that can be enumerated has aliphatic diisocyanate, alicyclic diisocyanate, aromatic series two different
Cyanate, aliphatic triisocyanate, polyisocyanates etc..
As aliphatic diisocyanate, for example, trimethylene diisocyanate, tetramethylene diisocyanate, Asia
Amyl diisocyanate, 1, hexamethylene-diisocyanate, 1,2- trimethylene diisocyanate, 1,2- tetramethylene diisocyanate, 2,
3- tetramethylene diisocyanate, 1,3- tetramethylene diisocyanate, 2,4,4- or 2,2,4- trimethyls 1, hexamethylene-diisocyanate,
2,6- diisocyanate base methyl caproates etc..As the example of alicyclic diisocyanate, it is different that 1,3- pentamethylene two can be enumerated
Cyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 1,3- cyclohexane diisocyanate, 3- isocyanatomethyl -3,5,5- trimethyl
Cyclohexyl isocyanate (alias: isophorone diisocyanate), 4,4 '-methylene two (cyclohexyl isocyanate), methyl -2,
Bis- (isocyanatomethyl) hexamethylenes of 4- cyclohexane diisocyanate, methyl -2,6- cyclohexane diisocyanate, 1,3-, 1,3-
Bis- (ethyl isocyanate base) hexamethylenes of bis- (ethyl isocyanate base) hexamethylenes, Isosorbide-5-Nitrae-, 2,5- or 2,6- bis- (isocyanatomethyl)
Norbornane (NBDI) and its mixture etc..
It as the example of aromatic diisocyanate, can enumerate: 2,4- toluene di-isocyanate(TDI)s and 2,6- toluene two
The isomer mixture of isocyanates and the toluene di-isocyanate(TDI), 4,4 '-'-diphenylmethane diisocyanates, 2,4 '-two
Phenylmethane diisocyanate and 2,2 '-'-diphenylmethane diisocyanates and the '-diphenylmethane diisocyanate it is arbitrary
Isomer mixture, toluene di-isocyanate(TDI), to phenylene diisocyanate, naphthalene diisocyanate etc..As three isocyanide of aliphatic
The example of acid esters can enumerate 1,3,6- triisocyanate methyl hexanes etc..As polyisocyanates, can enumerate mostly sub-
Methyl polyphenyl polyisocyanate, the polyisocyanates as derived from above-mentioned diisocyanate cpd.As by above-mentioned two isocyanide
The polyisocyanates of acid ester derivative has isocyanuric acid esters polyisocyanates, biuret class polyisocyanates, carbamates
Polyisocyanates, allophanic acid esters polyisocyanates, carbon imidodicarbonic diamide class polyisocyanates etc..It is preferable to use MDI.
The preparation method of hard polyurethane foam material of the invention does not carry out particular determination, according to art technology
Conventional method known to personnel carries out foaming preparation.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, it is purchased from traditional Chinese medicines chemical reagent.
Embodiment
Embodiment 1A kind of foam stabiliser that can be used for full water foamed system is provided, the foam stabiliser is to be modified
Polyether grafting organic silicon surfactant；The preparation method of the modified polyether grafted-organosilicon surfactant includes following step
It is rapid:
1) 50g silicon oil of low hydrogen content, 95g unsaturated polyether, 20g diethylene glycol (DEG) and 5mg platinum rhodium complex solution are added and are reacted
In kettle, it is 110 DEG C, under normal pressure in reaction temperature, reacts 4 hours, obtain intermediate product；
2) sulfonation processing is carried out to the intermediate product in the 1) step: potassium bisulfite is dissolved in the intermediate product different
In the mixed solution of third alcohol and water, and react 4 hours at 80 DEG C, then by be evaporated under reduced pressure away mixed solvent to get.
The unsaturated polyether is the allyl alcohol polyether HMS-229R (hydroxyl value about 130) of Zhejiang Real Madrid Chemical Co., Ltd.；
The volume ratio of the isopropanol and water is 2:1；The weight ratio of the potassium bisulfite and intermediate product is 1:20.
The preparation method of the silicon oil of low hydrogen content includes the following steps:
By 100g octamethylcy-clotetrasiloxane, 5.6g hexamethyldisiloxane, the methyl height that 30.6g hydrogen content is 1.55%
Containing hydrogen silicone oil and 8g Emathlite are added in reaction kettle, are heated to 45 DEG C of reactions and obtain within 12 hours hydrogen content be that 0.35% low contains
Hydrogen amount silicone oil.
This example additionally provides a kind of hard polyurethane foam material, prepares raw material, in parts by weight, including such as the following group
Point:
Full water combined polyether 100
Isocyanates 125
Stabilizer 1.5；
The stabilizer is the foam stabiliser that can be used for full water foamed system as described above；The full water combined polyether
Using the full water combined polyether BT-328W (including polyether polyol, catalyst and water) of the Science and Technology Ltd. of the primary scholar in Zhongshan city；
The isocyanates is MDI.
Embodiment 2A kind of foam stabiliser that can be used for full water foamed system is provided, the foam stabiliser is to be modified
Polyether grafting organic silicon surfactant；The preparation method of the modified polyether grafted-organosilicon surfactant includes following step
It is rapid:
1) 50g silicon oil of low hydrogen content, 181g unsaturated polyether, 35g diethylene glycol (DEG) and 16.5mg platinum rhodium complex are added and are reacted
In kettle, it is 120 DEG C, under normal pressure in reaction temperature, reacts 3 hours, obtain intermediate product；
2) phosphatizing treatment is carried out to the intermediate product in the 1) step: the intermediate product and phosphoric acid is added to reaction kettle
In, the toluene dissolution of the 50wt% of monomer gross mass is then added, and under conditions of being passed through nitrogen, 90 DEG C of insulation reactions 5 are small
When, then by crude product at 80 DEG C, vacuum distillation is purified under 0.08MPa to obtain the final product.
The unsaturated polyether is allyl polyethenoxy polyoxypropylene epoxy group ether, is purchased from the limited public affairs of Historic Area of Zhongshan in Nanjing City chemical industry
The HY series of products (molecular weight 800) of department；The weight ratio of the intermediate product and phosphoric acid is 27:1.
The preparation method of the silicon oil of low hydrogen content includes the following steps:
By 100g octamethylcy-clotetrasiloxane, 3.4g hexamethyldisiloxane, the methyl height that 27.5g hydrogen content is 1.55%
Containing hydrogen silicone oil and 8g Emathlite are added in reaction kettle, be heated to 45 DEG C of reactions obtain within 12 hours hydrogen content for 0.32% it is low
Containing hydrogen silicone oil.
This example additionally provides a kind of hard polyurethane foam material, prepares raw material, in parts by weight, including such as the following group
Point:
Full water combined polyether 100
Isocyanates 135
Stabilizer 2；
The stabilizer is the foam stabiliser that can be used for full water foamed system as described above；The full water combined polyether
Using the full water combined polyether B607 (including polyether polyol, catalyst and water) of the Science and Technology Ltd. of the primary scholar in Zhongshan city；Institute
Stating isocyanates is MDI.
Embodiment 3A kind of foam stabiliser that can be used for full water foamed system is provided, the foam stabiliser is to be modified
Polyether grafting organic silicon surfactant；The preparation method of the modified polyether grafted-organosilicon surfactant includes following step
It is rapid:
1) 50g silicon oil of low hydrogen content, 155g unsaturated polyether, 24g diethylene glycol (DEG) and 12.5mg platinum rhodium complex are added and are reacted
In kettle, it is 120 DEG C, under normal pressure in reaction temperature, reacts 3 hours, obtain intermediate product；
2) phosphatizing treatment is carried out to the intermediate product in the 1) step: the intermediate product and phosphoric acid is added to reaction kettle
In, the toluene dissolution of the 50wt% of monomer gross mass is then added, and under conditions of being passed through nitrogen, 90 DEG C of insulation reactions 5 are small
When, then by crude product at 80 DEG C, vacuum distillation is purified under 0.08MPa to obtain the final product.
The weight ratio of the intermediate product and phosphoric acid is 16:1；The unsaturated polyether is the limited public affairs of Zhejiang Real Madrid chemical industry
The HY series allyl polyethenoxy of allyl alcohol polyether HMS-232R (hydroxyl value about 75) and Historic Area of Zhongshan in Nanjing City Chemical Co., Ltd. of department
The mixing of polyoxypropylene epoxy group ether (molecular weight 550), weight ratio 2:1.
The preparation method of the silicon oil of low hydrogen content includes the following steps:
By 100g octamethylcy-clotetrasiloxane, 3.4g hexamethyldisiloxane, the methyl height that 27.5g hydrogen content is 1.55%
Containing hydrogen silicone oil and 8g Emathlite are added in reaction kettle, be heated to 45 DEG C of reactions obtain within 12 hours hydrogen content for 0.32% it is low
Containing hydrogen silicone oil.
This example additionally provides a kind of hard polyurethane foam material, prepares raw material, in parts by weight, including such as the following group
Point:
Full water combined polyether 100
Isocyanates 135
Stabilizer 2；
The stabilizer is the foam stabiliser that can be used for full water foamed system as described above；The full water combined polyether
Using the full water combined polyether B705 (including polyether polyol, catalyst and water) of the Science and Technology Ltd. of the primary scholar in Zhongshan city.Institute
Stating isocyanates is MDI.
Embodiment 4A kind of foam stabiliser that can be used for full water foamed system is provided, the foam stabiliser is to be modified
Polyether grafting organic silicon surfactant；The preparation method of the modified polyether grafted-organosilicon surfactant includes following step
It is rapid:
1) 50g silicon oil of low hydrogen content, 155g unsaturated polyether, 24g diethylene glycol (DEG) and 12.5mg platinum rhodium complex are added and are reacted
In kettle, it is 120 DEG C, under normal pressure in reaction temperature, reacts 3 hours, obtain intermediate product；
2) phosphatizing treatment is carried out to the intermediate product in the 1) step: the intermediate product and phosphoric acid is added to reaction kettle
In, the toluene dissolution of the 50wt% of monomer gross mass is then added, and under conditions of being passed through nitrogen, 90 DEG C of insulation reactions 5 are small
When, then by crude product at 80 DEG C, vacuum distillation is purified under 0.08MPa to obtain the final product.
The weight ratio of the intermediate product and phosphoric acid is 16:1；The unsaturated polyether is the limited public affairs of Zhejiang Real Madrid chemical industry
The HY series allyl polyethenoxy of allyl alcohol polyether HMS-229R (hydroxyl value about 130) and Historic Area of Zhongshan in Nanjing City Chemical Co., Ltd. of department
The mixing of polyoxypropylene epoxy group ether (molecular weight 550), weight ratio 2:1.
The silicon oil of low hydrogen content is the high containing hydrogen silicone oil of methyl, hydrogen content 1.55%.
This example additionally provides a kind of hard polyurethane foam material, prepares raw material, in parts by weight, including such as the following group
Point:
Full water combined polyether 100
Isocyanates 135
Stabilizer 2；
The stabilizer is the foam stabiliser that can be used for full water foamed system as described above；The full water combined polyether
Using the full water combined polyether B705 (including polyether polyol, catalyst and water) of the Science and Technology Ltd. of the primary scholar in Zhongshan city.Institute
Stating isocyanates is MDI.
Embodiment 5A kind of foam stabiliser that can be used for full water foamed system is provided, the foam stabiliser is to be modified
Polyether grafting organic silicon surfactant；The preparation method of the modified polyether grafted-organosilicon surfactant includes following step
It is rapid:
1) 50g silicon oil of low hydrogen content, 155g unsaturated polyether, 24g diethylene glycol (DEG) and 12.5mg platinum rhodium complex are added and are reacted
In kettle, it is 120 DEG C, under normal pressure in reaction temperature, reacts 3 hours, obtain intermediate product；
2) phosphatizing treatment is carried out to the intermediate product in the 1) step: the intermediate product and phosphoric acid is added to reaction kettle
In, the toluene dissolution of the 50wt% of monomer gross mass is then added, and under conditions of being passed through nitrogen, 90 DEG C of insulation reactions 5 are small
When, then by crude product at 80 DEG C, vacuum distillation is purified under 0.08MPa to obtain the final product.
The weight ratio of the intermediate product and phosphoric acid is 16:1；The unsaturated polyether is the limited public affairs of Zhejiang Real Madrid chemical industry
The HY series allyl polyethenoxy of allyl alcohol polyether HMS-229R (hydroxyl value about 130) and Historic Area of Zhongshan in Nanjing City Chemical Co., Ltd. of department
The mixing of polyoxypropylene epoxy group ether (molecular weight 550), weight ratio 2:1.
The preparation method of the silicon oil of low hydrogen content includes the following steps:
100g octamethylcy-clotetrasiloxane, the high containing hydrogen silicone oil of methyl that 27.5g hydrogen content is 1.55% and 8g acidity is white
Soil is added in reaction kettle, is heated to 45 DEG C of reactions 12 hours to obtain the final product.
This example additionally provides a kind of hard polyurethane foam material, prepares raw material, in parts by weight, including such as the following group
Point:
Full water combined polyether 100
Isocyanates 135
Stabilizer 2；
The stabilizer is the foam stabiliser that can be used for full water foamed system as described above；The full water combined polyether
Using the full water combined polyether B705 (including polyether polyol, catalyst and water) of the Science and Technology Ltd. of the primary scholar in Zhongshan city.Institute
Stating isocyanates is MDI.
Embodiment 6A kind of hard polyurethane foam material is provided, raw material is prepared, in parts by weight, including such as the following group
Point:
Full water combined polyether 100
Isocyanates 135
Stabilizer 2；
The stabilizer is the H-3565B of the high chemical industry in middle Shandong；The full water combined polyether uses the section of the primary scholar in Zhongshan city
The full water combined polyether B705 (including polyether polyol, catalyst and water) of skill Co., Ltd.The isocyanates is MDI.
Embodiment 7A kind of foam stabiliser that can be used for full water foamed system is provided, the foam stabiliser is to be modified
Polyether grafting organic silicon surfactant；The preparation method of the modified polyether grafted-organosilicon surfactant includes following step
It is rapid:
1) 50g silicon oil of low hydrogen content, 155g unsaturated polyether, 24g diethylene glycol (DEG) and 12.5mg platinum rhodium complex are added and are reacted
In kettle, reaction temperature be 120 DEG C, under normal pressure, react 3 hours to get.
The unsaturated polyether be Zhejiang Real Madrid Chemical Co., Ltd. allyl alcohol polyether HMS-229R (hydroxyl value about 130) and
The HY series allyl polyethenoxy polyoxypropylene epoxy group ether (molecular weight 550) of Historic Area of Zhongshan in Nanjing City Chemical Co., Ltd. mixes
It closes, weight ratio 2:1.
The preparation method of the silicon oil of low hydrogen content includes the following steps:
By 100g octamethylcy-clotetrasiloxane, 3.4g hexamethyldisiloxane, 202 first that 27.5g hydrogen content is 1.55%
The high containing hydrogen silicone oil of base and 8g Emathlite are added in reaction kettle, are heated to 45 DEG C of reactions and obtain within 12 hours hydrogen content be 0.32%
Silicon oil of low hydrogen content.
This example additionally provides a kind of hard polyurethane foam material, prepares raw material, in parts by weight, including such as the following group
Point:
Full water combined polyether 100
Isocyanates 135
Stabilizer 2；
The stabilizer is the foam stabiliser that can be used for full water foamed system as described above；The full water combined polyether
Using the full water combined polyether B705 (including polyether polyol, catalyst and water) of the Science and Technology Ltd. of the primary scholar in Zhongshan city.Institute
Stating isocyanates is MDI.
Comparative example 1A kind of hard polyurethane foam material is provided, raw material is prepared, in parts by weight, including such as the following group
Point:
Full water combined polyether 100
Isocyanates 135
Stabilizer 2；
The stabilizer is silicone surfactant B 8444；The full water combined polyether uses the section of the primary scholar in Zhongshan city
The full water combined polyether B705 (including polyether polyol, catalyst and water) of skill Co., Ltd.The isocyanates is MDI.
Performance evaluation
The physical property that can be used for the foam stabiliser of full water foamed system compares, and compares it thoroughly according to its transparency subjectivity
The transparency of lightness, the foam stabiliser that can be used for full water foamed system that discovery Examples 1 to 3 provides is fine, embodiment 4,
The transparency in 5,7 is preferably.
In foaming process, under identical material temperature, environment temperature, measures the cream time of hard polyurethane foam material, coagulates
The glue time does not glue the time and freely steeps density, as a result as shown in the table.
The active contrast table of table 1
The mobility for the stabilizer that embodiment and comparative example provides is compared, while testing thermal coefficient, foam table
Whether the foam structure in face (according to surface has whether air pocket, abscess are uniform, whether structure is regular to judge the good of foam structure
Bad situation comments 1~5 grade, wherein 1 grade of surface cells is least regular, worst, 5 points of foam surface performances are best) etc. parameters, knot
Fruit is as shown in the table.
The comparison of 2 mobility of table
It is fine from the stablizing effect for the foam stabiliser that can be seen that in above table in Examples 1 to 3.With lower
Foam free density and shorter not viscous time, corresponding polyurethane foamed material can be prepared using faster speed of production,
Phenomena such as foam interior cracking will not occur, can save time and preparation cost, improve production efficiency.Furthermore embodiment
Foam stabiliser in 1~3 is in polyurethane foamed material in application, foam during can be very good steady production, tool
While having higher foam height, it is close to symbolize material abscess in foaming process from side for foam wt with higher
It is regular to spend uniform cell structure size.And have from the stabilizer that can also be seen that in above table in Examples 1 to 3 higher
Flow index, better foam surface performance.
At last it is pointed out that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not intended to limit the invention, it is all at this
Made any modifications, equivalent replacements, and improvements etc., should be included in protection model of the invention within the spirit and principle of invention
Within enclosing.
Claims (10)
1. a kind of foam stabiliser that can be used for full water foamed system, which is characterized in that the foam stabiliser is modified polyether
Grafted-organosilicon surfactant；The body material for preparing of the modified polyether grafted-organosilicon surfactant includes low hydrogeneous
Silicone oil and unsaturated polyether, weight ratio are 1:(1~10).
2. can be used for the foam stabiliser of full water foamed system as described in claim 1, which is characterized in that the low Silicon Containing Hydrogen
The hydrogen content of oil is 0.05~0.8wt%.
3. can be used for the foam stabiliser of full water foamed system as described in claim 1, which is characterized in that the low Silicon Containing Hydrogen
The raw material for preparing of oil includes octamethylcy-clotetrasiloxane, hexamethyldisiloxane and high containing hydrogen silicone oil.
4. can be used for the foam stabiliser of full water foamed system as described in claim 1, which is characterized in that the modified polyether
The preparation method of grafted-organosilicon surfactant includes the following steps:
1) silicon oil of low hydrogen content, unsaturated polyether, dispersing agent and complex metal catalyst are added in reaction kettle, are in reaction temperature
It 80-120 DEG C, under normal pressure, reacts 2-8 hours, obtains intermediate product；
2) sulfonation processing and/or phosphatizing treatment are carried out to obtain the final product to the intermediate product in the 1) step.
5. can be used for the foam stabiliser of full water foamed system as claimed in claim 4, which is characterized in that described unsaturated poly-
Ether is allyl alcohol polyether and/or allyl polyethenoxy polyoxypropylene epoxy group ether.
6. can be used for the foam stabiliser of full water foamed system as claimed in claim 4, which is characterized in that the sulfonation processing
Include the following steps:
Potassium bisulfite and the intermediate product are dissolved in the mixed solution of isopropyl alcohol and water, and reacted at 70~80 DEG C
It 2~6 hours, discharges to obtain the final product；The volume ratio of the isopropanol and water is (2~10): 1.
7. can be used for the foam stabiliser of full water foamed system as claimed in claim 6, which is characterized in that the bisulfite
The weight ratio of potassium and intermediate product is 1:(5~60).
8. can be used for the foam stabiliser of full water foamed system as claimed in claim 4, which is characterized in that at the phosphorylation
Reason includes the following steps:
The intermediate product and phosphoric acid are added in reaction kettle, the toluene that 50~60wt% of monomer gross mass is then added is molten
Solution, and under conditions of being passed through nitrogen, 90~100 DEG C insulation reaction 3~5 hours, then handle to obtain the final product.
9. can be used for the foam stabiliser of full water foamed system as claimed in claim 8, which is characterized in that the intermediate product
Weight ratio with phosphoric acid is (8~30): 1.
10. a kind of hard polyurethane foam material, which is characterized in that it prepares raw material, in parts by weight, including following component:
Full water combined polyether 100
Isocyanates 125~150
Stabilizer 1.5~3；
The stabilizer is the foam stabiliser that can be used for full water foamed system as described in claim 1~8 any one.
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| CN111004396A (en) * | 2019-12-27 | 2020-04-14 | 江苏美思德化学股份有限公司 | Tertiary amino modified organic silicon polyether copolymer and preparation method and application thereof |
| CN111116922A (en) * | 2019-12-30 | 2020-05-08 | 江苏奥克化学有限公司 | Preparation method and application of phosphorus-containing polyether modified organic silicon flatting agent |
| CN111328821A (en) * | 2020-03-03 | 2020-06-26 | 上海悦联生物科技有限公司 | Bactericide composition containing pyraclostrobin and mancozeb |
| CN113105664A (en) * | 2021-03-17 | 2021-07-13 | 珠海东诚新材料股份有限公司 | Polyurethane foam stabilizer |
| CN113881419A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Foam liquid discharging agent composition for high-condensate gas well and preparation method and application thereof |
| CN115044217A (en) * | 2022-06-29 | 2022-09-13 | 成都交通投资集团有限公司 | High-viscoelasticity modified asphalt suitable for diversified climates |
| CN115073745A (en) * | 2022-07-01 | 2022-09-20 | 安徽恒光聚氨酯材料有限公司 | Novel environment-friendly antioxidant modified silicone oil and preparation method thereof |
| CN116217875A (en) * | 2023-03-22 | 2023-06-06 | 上海凯众汽车零部件有限公司 | Low-density polyurethane foam material for automobile carpet |
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| CN111004396A (en) * | 2019-12-27 | 2020-04-14 | 江苏美思德化学股份有限公司 | Tertiary amino modified organic silicon polyether copolymer and preparation method and application thereof |
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| CN111116922A (en) * | 2019-12-30 | 2020-05-08 | 江苏奥克化学有限公司 | Preparation method and application of phosphorus-containing polyether modified organic silicon flatting agent |
| CN111328821A (en) * | 2020-03-03 | 2020-06-26 | 上海悦联生物科技有限公司 | Bactericide composition containing pyraclostrobin and mancozeb |
| CN113881419A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Foam liquid discharging agent composition for high-condensate gas well and preparation method and application thereof |
| CN113881419B (en) * | 2020-07-02 | 2023-04-07 | 中国石油化工股份有限公司 | Foam liquid discharging agent composition for high-condensate gas well and preparation method and application thereof |
| CN113105664A (en) * | 2021-03-17 | 2021-07-13 | 珠海东诚新材料股份有限公司 | Polyurethane foam stabilizer |
| CN115044217A (en) * | 2022-06-29 | 2022-09-13 | 成都交通投资集团有限公司 | High-viscoelasticity modified asphalt suitable for diversified climates |
| CN115073745A (en) * | 2022-07-01 | 2022-09-20 | 安徽恒光聚氨酯材料有限公司 | Novel environment-friendly antioxidant modified silicone oil and preparation method thereof |
| CN115073745B (en) * | 2022-07-01 | 2023-09-15 | 安徽恒光聚氨酯材料有限公司 | Environment-friendly antioxidant modified silicone oil and preparation method thereof |
| CN116217875A (en) * | 2023-03-22 | 2023-06-06 | 上海凯众汽车零部件有限公司 | Low-density polyurethane foam material for automobile carpet |
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