CN107011507A - A kind of preparation and its application of organosilicon modified polyether polyalcohol - Google Patents
A kind of preparation and its application of organosilicon modified polyether polyalcohol Download PDFInfo
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- CN107011507A CN107011507A CN201710337958.3A CN201710337958A CN107011507A CN 107011507 A CN107011507 A CN 107011507A CN 201710337958 A CN201710337958 A CN 201710337958A CN 107011507 A CN107011507 A CN 107011507A
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds 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
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
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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
- 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
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen 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
- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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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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- 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
- C08G2280/00—Compositions for creating shape memory
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- Chemical Kinetics & Catalysis (AREA)
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- Polyurethanes Or Polyureas (AREA)
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Abstract
Invention is related to synthesis and the preparing technical field of new chemical materialses, disclose a kind of preparation and its application of organosilicon modified polyether polyalcohol, the advantage of silicones and PPG effectively can be carried out chemical fusion by this method, without additionally adding inorganic high-low temperature resistant material, this method is substantially superior to the method that tradition prepares polyurethane memory sponge.
Description
Technical field
The present invention relates to the synthesis of new chemical materialses and preparing technical field, particularly a kind of organosilicon modified polyether is polynary
The preparation and its application of alcohol.
Background technology
Polyurethane memory sponge, also known as " slow-recovery sponge ", deforms upon when being acted on by external force, sponge when external force disappears
Slowly automatic it can restore, whole process is as by having remembered, the material is widely used to health care, furniture clothes and work
The fields such as industry packaging.
The preparation main component of polyurethane slow rebound sponge is the special PPG of low resilience and organic isocyanate, its
The characteristics of species of middle slow-rebound polyether polyol determines slow-recovery sponge.Current slow-rebound polyether polyol species both at home and abroad
Various, hydroxyl value about 100-300 mg KOH/g, molecular weight is how interval in 600-2000.
The main feature of slow-rebound polyether polyol is exactly that applicability is wider both at home and abroad at present, and downstream is supporting more perfect；Deposit
Deficiency be mainly that product quality is poor, performance is single, and mainly the skeleton such as carbon, oxygen atom is constituted, generally existing polyurethane
Slow-recovery sponge is to temperature more sensitive, the low phenomenon of resistance to persistence.When polyurethane slow rebound sponge is influenced by temperature larger,
Can have that compliance is poor, water and oil-resistant reduction, low-temperature toughness increase, the increase of resilience time, high temperature hardness reduction, resilience time
The shortcomings of shortening, this just limits its application significantly.
With scientific and technological progress and the development of polyurethane industrial, requirement of the people to polyurethane material is more and more harsher, single
The material of superior performance can not meet social production and demand for development, and the comprehensive material of excellent performance gains great popularity.It is organic
Silicon possesses certain high and low temperature resistance, not only possesses the compliance of organosilicon and resistance to by slow-rebound polyether polyol of its modification
High and low temperature, the more viscoplasticity for slow-rebound polyether polyol.
The content of the invention
It is an object of the invention to provide a kind of preparation and its application of organosilicon modified polyether polyalcohol, organosilicon is solved
Modified polyether polylol preparation method, next solves application of the slow-rebound polyether polyol in polyurethane memory sponge, weight
Point solves resistance to persistence, pressure-resistant compression deformation and the resistant of high or low temperature of polyurethane slow rebound sponge.
To realize above-mentioned technical purpose and the technique effect, the invention discloses a kind of organosilicon modified polyether is many
The preparation of first alcohol, includes following steps：
Step 1：By the allyl alcohol compound and epoxide of carbon number C3~8, in base catalyst, polymerisation temperature
Polymerisation occurs under 105~125 DEG C of degree, 200~500Kpa of pressure, allyl polyether polyalcohol is generated；
Step 2：By the allyl polyether monomeric polyol and hydrogeneous silicon composition obtained by step 1, in acidic catalyst, plus
Into 100~120 DEG C of reaction temperature, under the protection of 0~500Kpa of reaction pressure nitrogen, occur addition reaction, prepare organosilicon and change
Property PPG.
Wherein, the allyl alcohol compound of carbon number C3~8 is allyl alcohol, methallyl alcohol, 2,2- bis-（Pi-allyl oxygen
Methyl）One or more mixtures in-n-butyl alcohol, Isosorbide-5-Nitrae-butylene glycol, epoxide component is expoxy propane, epoxy
It is one or more in ethane, epoxy butane, base catalyst be sodium hydroxide, sodium methoxide, potassium hydroxide it is one or more
Mixture.
Wherein, hydrogeneous silicon composition is that active hydrogen content is 0.75-1.55 mass fractions, hydrogen degree of functionality 2-6, hydrogeneous
Silicon composition backbone structure is silica segment, and side chain is saturated fat carbochain, and acidic catalyst is that chloroplatinic acid-isopropanol is molten
One or more compositions in liquid, the concentrated sulfuric acid.
The invention also discloses a kind of organosilicon modified polyether polyalcohol on prepared by temperature tolerance polyurethane memory sponge
Using preparing organosilicon modified polyether polyalcohol using above-mentioned preparation method, comprise the following steps：
Step 1：Weigh 30~50 parts of organosilicon modified polyether polyalcohol, basic polyether polyalcohol 30~50 respectively by weight
Part, 10~30 parts of polymer polyatomic alcohol, 0.28~0.4 part of amines catalyst, 0.08~1.2 part of tin catalyst, surface-active
0.8~1.2 part of agent silicone oil, 1.0~3.5 parts of pore-creating agent, 1.2~1.6 parts of foaming agent, are successively mixed evenly, and constant temperature 25 ±
0.5 DEG C is recorded as component A；
Step 2：25~75 parts of isocyanates is weighed by weight, is recorded as B component, and by component A and B component high-speed stirred
Lower 6-8s, pours into 50 DEG C of reaction die for molding, prepares polyurethane memory sponge.
Wherein, organosilicon modified polyether polyalcohol hydroxyl value is 100~280mgKOH/g, and mean molecule quantity is 700~2000,
Degree of functionality f=2.8~3.6,300~800mp.s of viscosity, 0.01~0.05mgKOH/g of acid number.
Wherein, isocyanates is that toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, polymeric diphenylmethane two are different
One or more compositions in cyanate.
Wherein, basic polyether polyalcohol is PPOX vinethene, and hydroxyl value is 56 ± 2 mgKOH/g, and degree of functionality 3 is put down
Average molecular weight 3000, polymer polyatomic alcohol be styrene, acrylonitrile grafting PPG, index hydroxyl value 25-35 mgKOH/g,
Degree of functionality 3, mean molecule quantity 5000~6000, amines catalyst is 70% double (dimethylaminoethyl) ethers and 30% DPG
One or more compositions in the solution that is made into, the DPG solution of 33% triethylene diamine, tin catalyst is octanoic acid
Stannous T9, di-n-butyl tin laurate T12 one or more compositions, silicone oil surfactant are polysiloxanes series
One or more compositions, foaming agent is one or more compositions in water, dichloromethane, a fluorine dichloroethanes.
The invention has the advantages that：
1. the present invention is optimized by technical recipe, it is proposed that a kind of technique simply and readily control to prepare organosilicon modified polyether more
The method of first alcohol, and its application on prepared by resistant of high or low temperature polyurethane memory sponge, this method can effectively will be organic
The advantage of silicon-oxygen polymer and PPG carries out chemical fusion, without additionally adding inorganic high-low temperature resistant material, this method
Substantially it is superior to the method that tradition prepares polyurethane memory sponge.
2. factory formula and technique Jing Guo rationally designing, the special PPG of polyurethane slow rebound itself tool of preparation
Standby certain perforate effect, can be reduced or even without using pore-creating agent to a certain extent when preparing polyurethane memory sponge, can
Suitable for a variety of isocyanate systems such as TDI, modified MDI, polyurethane memory sponge is prepared by it, not only with conventional urethane
The characteristics of memory foam, preferable compliance, water and oil-resistant, resistant of high or low temperature are also equipped with, i.e., in -20 DEG C~60 DEG C models of temperature
Preferable low resilience characteristic is still remain in enclosing, is not in that low-temperature toughness increases, the resilience time increases, high temperature hardness reduction,
The phenomenons such as resilience time shortening.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.
Embodiment 1
Prepared the invention discloses a kind of preparation of organosilicon modified polyether polyalcohol and its in temperature tolerance polyurethane memory sponge
On application, include following steps：
Step 1：By the allyl alcohol compound and epoxide of carbon number C3~8, in base catalyst, polymerisation temperature
Polymerisation occurs under 105~125 DEG C of degree, 200~500Kpa of pressure, allyl polyether polyalcohol is generated；
Step 2：By the allyl polyether monomeric polyol and hydrogeneous silicon composition obtained by step 1, in acidic catalyst, plus
Into 100~120 DEG C of reaction temperature, under the protection of 0~500Kpa of reaction pressure nitrogen, occur addition reaction, prepare organosilicon and change
Property PPG.
Step 3：Weigh respectively by weight 30~50 parts of organosilicon modified polyether polyalcohol, basic polyether polyalcohol 30~
50 parts, 10~30 parts of polymer polyatomic alcohol, 0.28~0.4 part of amines catalyst, 0.08~1.2 part of tin catalyst, surface live
0.8~1.2 part of property agent silicone oil, 1.0~3.5 parts of pore-creating agent, 1.2~1.6 parts of foaming agent, are successively mixed evenly, constant temperature 25
± 0.5 DEG C is recorded as component A；
Step 4：25~75 parts of isocyanates is weighed by weight, is recorded as B component, and by component A and B component high-speed stirred
Lower 6-8s, pours into 50 DEG C of reaction die for molding, prepares polyurethane memory sponge.
Wherein, the allyl alcohol compound of carbon number C3~8 is allyl alcohol, methallyl alcohol, 2,2- bis-（Pi-allyl oxygen
Methyl）One or more mixtures in-n-butyl alcohol, Isosorbide-5-Nitrae-butylene glycol, epoxide component is expoxy propane, epoxy
It is one or more in ethane, epoxy butane, base catalyst be sodium hydroxide, sodium methoxide, potassium hydroxide it is one or more
Mixture.
Wherein, hydrogeneous silicon composition is that active hydrogen content is 0.75-1.55 mass fractions, hydrogen degree of functionality 2-6, hydrogeneous
Silicon composition backbone structure is silica segment, and side chain is saturated fat carbochain, and acidic catalyst is that chloroplatinic acid-isopropanol is molten
One or more compositions in liquid, the concentrated sulfuric acid.
Wherein, organosilicon modified polyether polyalcohol hydroxyl value is 100~280mgKOH/g, and mean molecule quantity is 700~2000,
Degree of functionality f=2.8~3.6,300~800mp.s of viscosity, 0.01~0.05mgKOH/g of acid number.
Wherein, isocyanates is that toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, polymeric diphenylmethane two are different
One or more compositions in cyanate.
Wherein, basic polyether polyalcohol is PPOX vinethene, and hydroxyl value is 56 ± 2 mgKOH/g, and degree of functionality 3 is put down
Average molecular weight 3000, polymer polyatomic alcohol be styrene, acrylonitrile grafting PPG, index hydroxyl value 25-35 mgKOH/g,
Degree of functionality 3, mean molecule quantity 5000~6000, amines catalyst is 70% double (dimethylaminoethyl) ethers and 30% DPG
One or more compositions in the solution that is made into, the DPG solution of 33% triethylene diamine, tin catalyst is octanoic acid
Stannous T9, di-n-butyl tin laurate T12 one or more compositions, silicone oil surfactant are polysiloxanes series
One or more compositions, foaming agent is one or more compositions in water, dichloromethane, a fluorine dichloroethanes.
Embodiment 2
The invention discloses a kind of preparation method of organosilicon modified polyether polyalcohol, comprise the following steps that：
333.8g methallyl alcohols, 8g sodium methoxides are added in the polymerization reaction kettle of stainless steel, 0.3~0.4MPa nitrogen displacement
3~5 times, oxygen content is within 0.5%, and 110~115 DEG C of controlling reaction temperature, 0.2~0.5MPa of pressure is continuously added to
1666.2g expoxy propane and ethylene oxide mixture（Oxirane accounts for 8.5%）, when pressure is without significant change, cool 80-90
DEG C add 16.7g 85% phosphate aqueous solution and 100g deionized waters, stirring 2 hours after, 110~120 DEG C of temperature control, vacuum 3~
5 hours abjection water and small molecule, obtain methallyl alcohol based polyether polyol.
9g chloroplatinic acid-aqueous isopropanol is added, 100~110 DEG C of controlling reaction temperature is continuously added to that 288.4g is hydrogeneous to be had
Machine silicon composition, active hydrogen content about 1.4（%, m/m）, insulation reaction 2 hours, vacuum outgas 30min obtains organic-silicon-modified
PPG.
Product index：Hydroxyl value 114mgKOH/g, viscosity 570mp.s (25 DEG C), the mgKOH/g of acid number 0.015, clear appearance
Transparent no suspended substance.
Embodiment 3：
The invention discloses a kind of preparation method of organosilicon modified polyether polyalcohol, comprise the following steps that：
248.8g allyl alcohols, 8g sodium methoxides are added in the polymerization reaction kettle of stainless steel, 0.3~0.4MPa nitrogen displacement 3~5
Secondary, oxygen content is within 0.5%, and 110~115 DEG C of controlling reaction temperature, 0.2~0.5MPa of pressure is continuously added to 1752g epoxies
Propane and ethylene oxide mixture（Oxirane accounts for 7.5%）, when pressure is without significant change, cool 80-90 DEG C of addition 16.7g
85% phosphate aqueous solution and 100g deionized waters, after stirring 2 hours, 110~120 DEG C of temperature control, the abjection water of vacuum 3~5 hours
And small molecule, obtain allyl alcohol based polyether polyol.
6.8g chloroplatinic acid-aqueous isopropanol is added, 100~110 DEG C of controlling reaction temperature is continuously added to that 264g is hydrogeneous to be had
Machine silicon composition, active hydrogen content about 1.48（%, m/m）, insulation reaction 2 hours, vacuum outgas 30min obtains organic-silicon-modified
PPG.
Product index：Hydroxyl value 106mgKOH/g, viscosity 670mp.s (25 DEG C), acid number 0.02mgKOH/g, clear appearance is saturating
Bright no suspended substance.
Embodiment 4：
The invention discloses a kind of preparation method of organosilicon modified polyether polyalcohol, comprise the following steps that：
470g Isosorbide-5-Nitraes-butylene glycol, 8g sodium methoxides are added in the polymerization reaction kettle of stainless steel, 0.3~0.4MPa nitrogen is put
Change 3~5 times, oxygen content is within 0.5%, and 110~115 DEG C of controlling reaction temperature, 0.2~0.5MPa of pressure is continuously added to
1532g expoxy propane and ethylene oxide mixture（Oxirane accounts for 8.0%）, when pressure is without significant change, cool 80-90 DEG C
16.7g 85% phosphate aqueous solution and 100g deionized waters is added, after stirring 2 hours, 110~120 DEG C of temperature control, vacuum 3~5
Hour abjection water and small molecule, obtain Isosorbide-5-Nitrae-butylene glycol based polyether polyol.
6.6g chloroplatinic acid-aqueous isopropanol is added, 100~110 DEG C of controlling reaction temperature is continuously added to that 215g is hydrogeneous to be had
Machine silicon composition, active hydrogen content about 1.26（%, m/m）, insulation reaction 2 hours, vacuum outgas 30min obtains organic-silicon-modified
PPG.
Product index：Hydroxyl value 136mgKOH/g, viscosity 620mp.s (25 DEG C), acid number 0.021mgKOH/g, clear appearance is saturating
Bright no suspended substance.
Embodiment 5：
The invention discloses a kind of preparation method of organosilicon modified polyether polyalcohol, comprise the following steps that：
114.8g methallyl alcohols, 172.2g allyl alcohols, 8g sodium methoxides are added in the polymerization reaction kettle of stainless steel, 0.3~
0.4MPa nitrogen displacement 3~5 times, oxygen content is within 0.5%, 110~115 DEG C of controlling reaction temperature, pressure 0.2~
0.5MPa, is continuously added to 1713g expoxy propane and ethylene oxide mixture（Oxirane accounts for 8.2%）, treat pressure without significant change
When, the 80-90 DEG C of addition 16.7g that cool 85% phosphate aqueous solution and 100g deionized waters, after stirring 2 hours, temperature control 110~
120 DEG C, vacuum deviates from water and small molecule in 3~5 hours, obtains allyl polyether polyalcohol.
7g chloroplatinic acid-aqueous isopropanol is added, 100~110 DEG C of controlling reaction temperature is continuously added to 325g hydrogeneous organic
Silicon composition, active hydrogen content about 1.4（%, m/m）, insulation reaction 2 hours, vacuum outgas 30min obtains organic-silicon-modified poly-
Ethoxylated polyhydric alcohol.
Product index：Hydroxyl value 110mgKOH/g, viscosity 580mp.s (25 DEG C), acid number 0.032mgKOH/g, clear appearance is saturating
Bright no suspended substance.
Embodiment 6：
The invention discloses a kind of application of organosilicon modified polyether polyalcohol on prepared by temperature tolerance polyurethane memory sponge, tool
Body step is as follows：
Step 1：Weigh 30~50 parts of organosilicon modified polyether polyalcohol, basic polyether polyalcohol 30~50 respectively by weight
Part, 0.28~0.4 part of amines catalyst, 0.08~1.2 part of tin catalyst, 0.8~1.2 part of silicone oil surfactant, perforate
1.0~3.5 parts of agent, 1.2~1.6 parts of foaming agent, are successively mixed evenly, and 25 ± 0.5 DEG C of constant temperature is recorded as component A；
Step 2：25~75 parts of isocyanates is weighed by weight, is recorded as B component, and by component A and B component high-speed stirred
Lower 6-8s, pours into 50 DEG C of reaction die for molding, prepares polyurethane memory sponge.
Wherein, organosilicon modified polyether polyalcohol is embodiment 2,3 preparation-obtained organosilicon modified polyethers in component A
Polyalcohol, basic polyether polyalcohol is the M-3031D PPGs that Meizhou Bay, Fujian chlor-alkali Co., Ltd produces, index hydroxyl value
56 mgKOH/g, mean molecule quantity about 3000, foaming agent is 1.2~1.6 parts of water, and the silicone oil surfactant trade mark is L-3002
0.8~1.2 part, amine catalyst is 0.28~0.4 part of the DPG solution of 33% triethylene diamine, and tin catalyst is two positive fourths
0.08~1.2 part of base tin laurate T12, B component is commercially available BAYER company's Ts DI-80 isocyanates.
The TDI system polyurethanes memory foam of table 1 reactivity and performance detection
The as shown by data of table 1：Organic-silicon-modified slow-rebound polyether polyol（Embodiment 2,3）, prepared TDI system polyurethanes note
Recall sponge, when the temperature is changed（- 10 DEG C increase to 25 DEG C, 60 DEG C）, not only sponge firmness change amplitude is small, i.e., to temperature not
Sensitivity, wherein commercially available common sponge firmness change amplitude is larger, i.e., it is more sensitive to temperature；And possess more excellent resistance to
Persistence, and relatively low hot compression permanent deformation.
Embodiment 7
A kind of application of organosilicon modified polyether polyalcohol on prepared by temperature tolerance polyurethane memory sponge, is comprised the following steps that：
Step 1：Weigh 30~50 parts of organosilicon modified polyether polyalcohol, basic polyether polyalcohol 30~50 respectively by weight
Part, 10~30 parts of polymer polyatomic alcohol, 0.28~0.4 part of amines catalyst, 0.08~1.2 part of tin catalyst, surface-active
0.8~1.2 part of agent silicone oil, 1.0~3.5 parts of pore-creating agent, 1.2~1.6 parts of foaming agent, are successively mixed evenly, and constant temperature 25 ±
0.5 DEG C is recorded as component A；
Step 2：25~75 parts of isocyanates is weighed by weight, is recorded as B component, and by component A and B component high-speed stirred
Lower 6-8s, pours into 50 DEG C of reaction die for molding, prepares polyurethane memory sponge.
Wherein, organosilicon modified polyether polyalcohol is embodiment 4,5 preparation-obtained organosilicon modified polyethers in component A
Polyalcohol, basic polyether polyalcohol is the M-3031D PPGs that Meizhou Bay, Fujian chlor-alkali Co., Ltd produces, index hydroxyl value
56 mgKOH/g, mean molecule quantity about 3000, polymer polyatomic alcohol is that Tianjin Petrochemical Company produces POP-2045, index hydroxyl value 28
MgKOH/g, mean molecule quantity about 6000.Foaming agent is 1.2~1.6 parts of water, and the silicone oil surfactant trade mark is L-3002 0.8
~1.2 parts, amine catalyst is 0.28~0.4 part of the DPG solution of 33% triethylene diamine, and tin catalyst is di-n-butyl month
0.08~1.2 part of cinnamic acid tin T12, B component is commercially available Huntsman companies Suprasec-3234 isocyanates（Modified MDI）.
The liquefied mdi system polyurethane memory foam of table 2 reactivity and performance detection
The as shown by data of table 2：Organic-silicon-modified slow-rebound polyether polyol（Embodiment 4,5）, the prepared poly- ammonia of liquefied mdi system
Ester memory foam, when the temperature is changed（- 10 DEG C increase to 25 DEG C, 60 DEG C）, not only sponge firmness change amplitude is small, i.e., to temperature
Degree is insensitive, wherein commercially available common sponge firmness change amplitude is larger, i.e., it is more sensitive to temperature；And possess more excellent
Resistance to persistence and relatively low hot pressing permanent deformation.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in,
It should all be included within the scope of the present invention.
Claims (7)
1. a kind of preparation of organosilicon modified polyether polyalcohol, it is characterised in that include following steps：
Step 1：By the allyl alcohol compound and epoxide of carbon number C3~8, in base catalyst, polymerisation temperature
Polymerisation occurs under 105~125 DEG C of degree, 200~500Kpa of pressure, allyl polyether polyalcohol is generated；
Step 2：By the allyl polyether monomeric polyol and hydrogeneous silicon composition obtained by step 1, in acidic catalyst, plus
Into 100~120 DEG C of reaction temperature, under the protection of 0~500Kpa of reaction pressure nitrogen, occur addition reaction, prepare organosilicon and change
Property PPG.
2. a kind of preparation of organosilicon modified polyether polyalcohol as claimed in claim 1, it is characterised in that：Described carbon atom
The allyl alcohol compound of number C3~8 is allyl alcohol, methallyl alcohol, 2,2- bis-（Allyloxymethyl）- n-butyl alcohol, 1,4- fourths
One or more mixtures in enediol, described epoxide component is expoxy propane, oxirane, epoxy butane
Middle one or more, described base catalyst is sodium hydroxide, sodium methoxide, one or more mixtures of potassium hydroxide.
3. a kind of preparation of organosilicon modified polyether polyalcohol as claimed in claim 1 or 2, it is characterised in that：Described contains
Hydrogen silicon composition is that active hydrogen content is 0.75-1.55 mass fractions, hydrogen degree of functionality 2-6, described hydrogeneous organosilicon group
Compound backbone structure is silica segment, and side chain is saturated fat carbochain, and described acidic catalyst is molten for chloroplatinic acid-isopropanol
One or more compositions in liquid, the concentrated sulfuric acid.
4. a kind of application of organosilicon modified polyether polyalcohol on prepared by temperature tolerance polyurethane memory sponge, it is characterised in that：
The organosilicon modified polyether polyalcohol prepared using the preparation method described in the claims any one of 1-3, including following step
Suddenly：
Step 1：Weigh 30~50 parts of organosilicon modified polyether polyalcohol, basic polyether polyalcohol 30~50 respectively by weight
Part, 10~30 parts of polymer polyatomic alcohol, 0.28~0.4 part of amines catalyst, 0.08~1.2 part of tin catalyst, surface-active
0.8~1.2 part of agent silicone oil, 1.0~3.5 parts of pore-creating agent, 1.2~1.6 parts of foaming agent, are successively mixed evenly, and constant temperature 25 ±
0.5 DEG C is recorded as component A；
Step 2：25~75 parts of isocyanates is weighed by weight, is recorded as B component, and by component A and B component high-speed stirred
Lower 6-8s, pours into 50 DEG C of reaction die for molding, prepares polyurethane memory sponge.
5. a kind of organosilicon modified polyether polyalcohol as claimed in claim 4 is on prepared by temperature tolerance polyurethane memory sponge
Using, it is characterised in that described organosilicon modified polyether polyalcohol hydroxyl value is 100~280mgKOH/g, and mean molecule quantity is
700~2000, degree of functionality f=2.8~3.6,300~800mp.s of viscosity, 0.01~0.05mgKOH/g of acid number.
6. a kind of organosilicon modified polyether polyalcohol as claimed in claim 5 is on prepared by temperature tolerance polyurethane memory sponge
Using, it is characterised in that described isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, polymerization hexichol
One or more compositions in dicyclohexylmethane diisocyanate.
7. a kind of organosilicon modified polyether polyalcohol as claimed in claim 6 is on prepared by temperature tolerance polyurethane memory sponge
Using, it is characterised in that described basic polyether polyalcohol is PPOX vinethene, and hydroxyl value is 56 ± 2 mgKOH/g, official
Energy degree 3, mean molecule quantity 3000, described polymer polyatomic alcohol is styrene, acrylonitrile grafting PPG, index hydroxyl value
25-35 mgKOH/g, degree of functionality 3, mean molecule quantity 5000~6000, double (dimethylaminos that described amines catalyst is 70%
Ethyl) solution that ether and 30% DPG are made into, one or more groups in the DPG solution of 33% triethylene diamine
Compound, described tin catalyst is stannous octoate T9, di-n-butyl tin laurate T12 one or more compositions, institute
The silicone oil surfactant stated is one or more compositions of polysiloxanes series, and described foaming agent is water, dichloromethane
One or more compositions in alkane, a fluorine dichloroethanes.
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| CN107652434A (en) * | 2017-10-16 | 2018-02-02 | 德清舒华泡沫座椅有限公司 | A kind of preparation method of organosilicon polyalcohol |
| CN108409971A (en) * | 2018-02-07 | 2018-08-17 | 江西三越新材料有限公司 | A kind of preparation method of organosilicon modified polyether polyalcohol |
| CN109265673A (en) * | 2018-09-26 | 2019-01-25 | 南京林业大学 | A kind of organosilicon modified polyether polyalcohol and its preparation method and application |
| CN109536106A (en) * | 2018-11-29 | 2019-03-29 | 上海东大化学有限公司 | A kind of high intensity silane modified polyether polymer and preparation method thereof |
| CN110527059A (en) * | 2019-07-31 | 2019-12-03 | 成都世友海绵制品有限公司 | A kind of low temperature perception memory foam and preparation method based on air and structural support |
| CN111944141A (en) * | 2020-08-25 | 2020-11-17 | 山东万达有机硅新材料有限公司 | Silane modified polyether and preparation method thereof |
| CN112142942A (en) * | 2020-09-24 | 2020-12-29 | 南通馨宇诺家居用品有限公司 | Washable antibacterial mildew-proof memory foam and application thereof |
| CN113603861A (en) * | 2021-08-12 | 2021-11-05 | 福州大学 | Antistatic low-temperature-resistant slow-rebound polyurethane sponge material and preparation method thereof |
| CN113621123A (en) * | 2021-09-07 | 2021-11-09 | 福州大学 | Antibacterial enhanced low-temperature-resistant slow-resilience polyurethane sponge and preparation method thereof |
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| CN109536106A (en) * | 2018-11-29 | 2019-03-29 | 上海东大化学有限公司 | A kind of high intensity silane modified polyether polymer and preparation method thereof |
| CN110527059A (en) * | 2019-07-31 | 2019-12-03 | 成都世友海绵制品有限公司 | A kind of low temperature perception memory foam and preparation method based on air and structural support |
| CN111944141A (en) * | 2020-08-25 | 2020-11-17 | 山东万达有机硅新材料有限公司 | Silane modified polyether and preparation method thereof |
| CN112142942A (en) * | 2020-09-24 | 2020-12-29 | 南通馨宇诺家居用品有限公司 | Washable antibacterial mildew-proof memory foam and application thereof |
| CN113603861A (en) * | 2021-08-12 | 2021-11-05 | 福州大学 | Antistatic low-temperature-resistant slow-rebound polyurethane sponge material and preparation method thereof |
| CN113603861B (en) * | 2021-08-12 | 2022-07-22 | 福州大学 | Antistatic low-temperature-resistant slow-rebound polyurethane sponge material and preparation method thereof |
| CN113621123A (en) * | 2021-09-07 | 2021-11-09 | 福州大学 | Antibacterial enhanced low-temperature-resistant slow-resilience polyurethane sponge and preparation method thereof |
| CN114479048A (en) * | 2021-12-22 | 2022-05-13 | 山东一诺威新材料有限公司 | Preparation method of polymer-based rigid foam polyether polyol |
| CN114479048B (en) * | 2021-12-22 | 2023-11-10 | 山东一诺威新材料有限公司 | Preparation method of polymer-based rigid foam polyether polyol |
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