CN110204729A - A kind of silicone copolymer surfactants and its purposes in liquefied natural gas heat preservation rigid foam - Google Patents
A kind of silicone copolymer surfactants and its purposes in liquefied natural gas heat preservation rigid foam Download PDFInfo
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- CN110204729A CN110204729A CN201910635329.8A CN201910635329A CN110204729A CN 110204729 A CN110204729 A CN 110204729A CN 201910635329 A CN201910635329 A CN 201910635329A CN 110204729 A CN110204729 A CN 110204729A
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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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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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
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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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Abstract
The present invention provides a kind of silicone copolymer surfactants, with following general formula: MDxD’yM；Wherein, M is selected from (CH3)3SiO1/2, (CH3)2R’SiO1/2Any one of；D is (CH3)2SiO2/2；D ' is (CH3)2(R) SiO2/2；X+y is that 8 ~ 30, y is 2 ~ 6.The present invention also provides above-mentioned organic silicon surfactants to prepare the application in liquefied natural gas heat preservation hard foamed poly urethane.A kind of flame retardant type organic silicon surfactant of polyurethane rigid foam plastic of the invention is applied in composition the performances such as the anti-flammability that can be obviously improved obtained liquefied natural gas hard polyurethane foam, compression strength, thermal coefficient, linear dimension change rate.
Description
Technical field
The present invention relates to chemical fields, especially relate to silicone copolymer surfactants, specifically a kind of organosilicon
Copolymer surfactants and its purposes in liquefied natural gas heat preservation rigid foam.
Background technique
With advances in technology with the raising of living standards of the people, liquefied natural gas (LNG), liquid oxygen (LO2), liquid nitrogen
(LN2), the application field of the cryogenic liquids compound such as liquefied petroleum gas (LPG) constantly expand, demand also constantly expands, especially
LNG.The main ingredient of LNG is methane, and natural gas is usually cooled to -163 DEG C under normal pressure state, is allowed to be condensed into liquid,
Volume after liquefaction is about the 1/600 of gaseous volume, therefore can greatly save storage and transportation space, improve conevying efficiency.LNG is one
Kind cleaning, the efficient energy, favor is increasingly received as clean energy resource, and many countries are using LNG as preferred fuels.China
The import volume of LNG in 2017 increased by 50% compared with 2016, and import volume is about 38,000,000 tons；A large amount of imports of LNG, bring LNG
The prosperity of the industry of transport and storage.
Rigid polyurethane foam has good heat-insulating property, while having lower density and good resistance to ultralow
Warm nature energy is more and more used for cold insulation of LNG field；Hard polyurethane foams pass through spraying application or technique for sticking application
In LNG tank body or pipe surface, outside heat can effectively be prevented to enter tank body, keep LNG in suitable temperature and pressure
Lower storage, transport, reduce the evaporation capacity of liquid.
However polyurethane foam plastics is a kind of high-molecular organic material, is haveed the shortcomings that inflammable；This to LNG transport,
Storage is brought great potential safety hazard.It is flame-retardant modified therefore, it is necessary to be carried out to rigid polyurethane foam.
Summary of the invention
The purpose of the present invention is to provide a kind of silicone copolymer surfactants, this Organosiliconcopolymere
It is inflammable that surfactant will solve polyurethane foam plastics in the prior art, has the technical issues of security risk.
The present invention provides a kind of silicone copolymer surfactants, it is characterised in that: it is with following general formula:
MDxD’yM；Wherein, M is selected from (CH3)3SiO1/2、(CH3)2R’SiO1/2Any one of；D is (CH3)2SiO2/2；D ' is (CH3)2
(R)SiO2/2,；X+y is that 8~30, y is 2~6；The R ' compound selected from the group below:
(1) at least one allyl polyethenoxy ether, general formula are as follows: CnH2n(C2H4O)a(C3H6O)bOH, weight average molecular weight are
200-700, it be 2~16, b is 2~16 that wherein n, which is 2~4, a, and polyethylene oxide section and polypropylene oxide segments in segment
Weight ratio is 60~100:0~40；
(2) at least one phenylacetylene base silane.
(3) molar ratio of phenylacetylene base silane and allyl polyethenoxy ether is 1:4~1:10.
Further, excessive allyl polyethenoxy ether weight percent is remained in silicone copolymer surfactants
It is 10~40%.
Further, the phenylacetylene base silane is tolans base silane, three phenylacetylene base silanes or four phenylacetylenes
Any one in base silane；
A. the structure of tolans base silane is as follows, in which: R1,R2For alkyl or aryl:
B. the structure of three phenylacetylene base silanes is as follows, in which: R be alkyl or aryl:
C. the structure of four phenylacetylene base silanes is as follows:
The present invention also provides above-mentioned organic silicon surfactants to prepare liquefied natural gas heat preservation rigid poly urethanes
Application in foams.
The present invention also provides a kind of polyurethane foam compositions of liquefied natural gas heat preservation, according to parts by weight
Meter, is mixed by following raw material:
The viscosity of above-mentioned polyurethane foam composition be 3000~5000mPa.s (25 DEG C), hydroxyl value be 250~
350mgKOH/g, moisture content weight content is less than 0.1%；
Further, the foaming agent is low-boiling foaming agent, such as 1,1,1,3,3- pentafluoropropane (HFC-245fa),
1,1,1,3,3- 3-pentafluorobutane (HFC-365mfc), chlorotrifluoropropylene (LBA), pentamethylene (CP), pentane (NP) etc., preferably
For LBA.
Further, the water is preferably deionized water.
Further, the fire retardant is polyurethane foam field conventional flame retardants, preferably three (2- chloropropyl) phosphorus
Acid esters (TCPP), three (2- chloroethyl) phosphates (TCEP), triethyl phosphate (TEP) or methyl-phosphoric acid dimethyl ester (DMMP), compared with
Good is TCPP.
Each component in the preparation, need to only had fool proof mix with composition by polyurethane foam of the present invention
It closes in kettle and uniformly mixes, when mixing preferably carries out in stainless steel mixing kettle, and incorporation time is preferably at 0.5~1 hour.
The application method of polyurethane foam composition of the present invention, polyurethane foam composition and isocyanates
It is mixed according to 1: 1.0~1: 2.0 ratio, preferable reaction ratio is 1: 1.0, is foamed using polyurethane coating foaming machine
Reaction molding, is made polyurethane foam.Wherein, isocyanates is preferably polymeric MDI, such as PM200, M20S, 44V20,5005.
The present invention should meet the construction process requirement of polyurethane coating during preparing polyurethane foam, such as:
(1) environment temperature is not less than 10 DEG C, is not higher than 35 DEG C；
(2) relative air humidity is not more than 85%；
(3) live wind speed is not more than 5m/s；
(4) substrate is sufficiently dry, and moisture content is not more than 8%；
A kind of flame retardant type organic silicon surfactant of polyurethane rigid foam plastic of the invention, is applied to combination
Anti-flammability, compression strength, thermally conductive system that obtained liquefied natural gas (LNG) uses hard polyurethane foam can be obviously improved in object
The performances such as number, linear dimension change rate.
The present invention is compared with prior art, its technical effect is that actively and apparent.The present invention is by introducing phenylacetylene base
Organic silicon surfactant made from silane resin can improve the anti-flammability and mechanical strength of hard polyurethane foams, while this hair
Bright liquefied natural gas (LNG) heat preservation hard polyaminoester composition can be directly used for liquefied natural gas deep cooling heat preservation industry,
The heat preservation of large-scale pipeline and tank body, cold insulation field.
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.
Organic silicon surfactant provided by the invention can be prepared by well known method, such as total with non-hydrolytic Si-C
Polymers reacts preparation with the allyl polyether of C=C double bond by the polysiloxanes containing Si-H.Platinum catalyst such as six water chlorine platinum
Acid (H2PtCl6·6H2O) there is particularly preferred catalytic effect；In addition, polysiloxanes-final molecule of polyoxyethylene branched chain copolymer
Structure also rely on reaction temperature, the activity of reactant, reactant ingredient proportion.To above-mentioned Organosiliconcopolymere surface-active
The structure of agent is only enumerated following 3 embodiments and is described in detail, and the silicone copolymer surfactants of other structures can also
To be prepared according to this method, will not enumerate.
Used in liquefied natural gas (LNG) heat preservation hard polyaminoester composition following tests example provided by the invention
Raw material sources are as follows:
Combined polyether glycol adopts self-control in the following method or is commercial product:
Combined polyether glycol contain polyether polyol, polyester polyol, catalyst,；Its viscosity is 400-600
MPa.s, hydroxyl value 200-300mgKOH/g, water content is less than 0.1%；
Combined polyether glycol 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.
The catalyst be tertiary amine catalyst and organo-metallic catalyst combination, the tertiary amine catalyst and
Organo-metallic catalyst mass ratio is 1:1；Further, the tertiary amine catalyst is the BX 405 of Evonik, and described has
Organic metal catalyst is isooctyl acid potassium, and the isooctyl acid potassium is that the mass percent of potassium ion is 15%.
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 glycol.
Surfactant LK221 is purchased from Evonik.
Surfactant L6900 is purchased from Momentive.
Polyurethane composite catalyst BX405 and K-15 are purchased from Evonik (winning wound industrial group).
Fire retardant TCPP is purchased from Jiangsu Yoke Technology Co., Ltd..
LBA is purchased from Honeywell.
Isocyanates is polymeric MDI, is purchased from Yantai Wanhua, model PM200.
The preparation of 1 silicone copolymer surfactants of embodiment
There is the four-hole boiling flask of fixed device, temperature incubation function, mechanical stirring, thermocouple and the 10L for being connected with nitrogen at one
In, the polyoxyethylene ether (referred to as polyethers A) that the average molecular weight of the methyl blocking of 1820g allyl alcohol starting is 350 is added, this is poly-
Ether A contains the ethylene oxide group that molar percentage is 100%；341g methyl famesoate is added, then will
The low hydrogen containing siloxane of 2140g (abbreviation MD9D’4M it) is added in four-hole boiling flask, starts to stir, using heating mantle heats to 90 DEG C,
Stirring 5 minutes, after chloroplatinic acid ethanol solution is added, so that concentration of the chloroplatinic acid in entire reaction system is 20ppm, instead
After answering 4 hours, as clear as crystal weak yellow liquid, as silicone copolymer surfactants are obtained.
The preparation of 2 silicone copolymer surfactants of embodiment
There is the four-hole boiling flask of fixed device, temperature incubation function, mechanical stirring, thermocouple and the 10L for being connected with nitrogen at one
In, the polyoxyethylene ether (referred to as polyethers B) that the average molecular weight of the methyl blocking of 2145g allyl alcohol starting is 550 is added, this is poly-
Ether B contains the propylene oxide base that the ethylene oxide group that molar percentage is 70% and molar percentage are 30%；It is added
Three phenylacetylene base silane of 227.1g methyl, then by the low hydrogen containing siloxane of 3051g (abbreviation MD22D’4M four-hole boiling flask) is added
In, start to stir, using heating mantle heats to 90 DEG C, stir 5 minutes, after chloroplatinic acid ethanol solution is added, so that chloroplatinic acid exists
Concentration in entire reaction system is 20ppm, after reaction 4 hours, obtains as clear as crystal weak yellow liquid, as organosilicon is total
Polymer surfactants.
The preparation of 3 silicone copolymer surfactants of embodiment
There is the four-hole boiling flask of fixed device, temperature incubation function, mechanical stirring, thermocouple and the 10L for being connected with nitrogen at one
In, the polyoxyethylene ether (referred to as polyethers C) that the average molecular weight of the methyl blocking of 3640g allyl alcohol starting is 700 is added, this is poly-
Ether C contains the propylene oxide base that the ethylene oxide group that molar percentage is 75% and molar percentage are 25%；It is added
Tetra- phenylacetylene base silane of 266g, then by the low hydrogen containing siloxane of 2165g (abbreviation MD12D’5M it) is added in four-hole boiling flask, starts
Stirring is stirred 5 minutes using heating mantle heats to 90 DEG C, after chloroplatinic acid ethanol solution is added, so that chloroplatinic acid is entirely reacting
Concentration in system is that 20ppm obtains as clear as crystal weak yellow liquid, as Organosiliconcopolymere table after reaction 4 hours
Face activating agent.
Test example 1
Select commercially available surfactantOrganosilicon LK221 as a comparison case 1, embodiment 1 is made as a control group
For ultralow temperature liquefied natural gas (LNG) heat preservation hard polyurethane ester polyurethane foam, specific implementation step is as follows:
(1) preparation of hard polyurethane foams composition
100 parts of combined polyether glycol, 5 parts of the organic silicon surfactant of embodiment 1,20 parts of foaming agent LBA, water 1.5
Part and 30 parts of fire retardant TCPP.
According to above-mentioned formula, each ingredient is added in stainless steel mixing kettle, it is small with the revolving speed stirring 1 of 500r/min at room temperature
When, blowing is up to polyurethane foam composition.
(2) preparation of polyurethane foam heat insulation material:
Polyurethane foam composition and isocyanates PM200 are used into spraying robot, according to the ratio of volume ratio 1: 1.0
Example preparation density is about 40kg/m3Polyurethane foam heat insulation material, the performance of the polyurethane foam is shown in Table 1.
Table 1:
Table 1 statistics indicate that, compared with comparative example, organic silicon surfactant provided by the invention liquefaction obtained is natural
Gas (LNG) heat preservation hard polyurethane foam has lower burning height and compared with high bond strength.
Test example 2
Select commercially available surfactantOrganosilicon LK221 as a comparison case 2, embodiment 2 is made as a control group
It is as follows for ultralow temperature hard polyurethane polyureas urethane foams, specific implementation step:
(1) preparation of polyurethane foam composition
100 parts of combined polyether glycol, 1 part of the organic silicon surfactant of embodiment 2,20 parts of foaming agent LBA, water 1.5
Part and 30 parts of fire retardant TCPP.
According to above-mentioned formula, each ingredient is added in stainless steel mixing kettle, it is small with the revolving speed stirring 1 of 500r/min at room temperature
When, blowing is up to polyurethane foam composition.
(2) preparation of polyurethane foam heat insulation material:
Polyurethane foam composition and isocyanates PM200 are used into spraying robot, according to the ratio of volume ratio 1: 1.0
Example preparation density is about 40kg/m3Polyurethane foam heat insulation material, the performance of the polyurethane foam is shown in Table 2.
Table 2:
Table 2 statistics indicate that, with compared with comparative example, the organic silicon surfactant provided by the invention day obtained that liquefies
Right gas (LNG) heat preservation hard polyurethane foam has lower burning height and compared with high bond strength.
Test example 3
Select commercially available surfactantOrganosilicon LK221 makes as a control group as comparative example 3, embodiment 3
It is as follows for ultralow temperature hard polyurethane polyureas urethane foams, specific implementation step:
(1) preparation of polyurethane foam composition
100 parts of combined polyether glycol, 2 parts of the organic silicon surfactant of embodiment 3,20 parts of foaming agent LBA, water 1.5
Part and 30 parts of fire retardant TCPP.
According to above-mentioned formula, each ingredient is added in stainless steel mixing kettle, it is small with the revolving speed stirring 1 of 500r/min at room temperature
When, blowing is up to polyurethane foam composition.
(2) preparation of polyurethane foam heat insulation material:
Polyurethane foam composition and isocyanates PM200 are used into spraying robot, according to the ratio of volume ratio 1: 1.0
Example preparation density is about 40kg/m3Polyurethane foam heat insulation material, the performance of the polyurethane foam is shown in Table 3.
Table 3:
Table 3 statistics indicate that, compared with comparative example, organic silicon surfactant provided by the invention liquefaction obtained is natural
Gas (LNG) heat preservation hard polyurethane foam has lower burning height and compared with high bond strength.
Test example 4:
Select commercially available organic silicon surfactantOrganosilicon L6900 is as comparative example 4, the conduct pair of embodiment 1
Ultralow temperature hard polyurethane polyureas urethane foams are prepared for according to group, specific implementation step is as follows:
(1) preparation of polyurethane foam composition
100 parts of combined polyether glycol, 2 parts of the organic silicon surfactant of embodiment 1,18 parts of foaming agent LBA, water 1.2
Part and 20 parts of fire retardant TCPP.
According to above-mentioned formula, each ingredient is added in stainless steel mixing kettle, it is small with the revolving speed stirring 1 of 500r/min at room temperature
When, blowing is up to polyurethane foam composition.
(2) preparation of polyurethane foam heat insulation material:
Polyurethane foam composition and isocyanates PM200 are used into spraying robot, according to the ratio of volume ratio 1: 1.0
Example preparation density is about 40kg/m3Polyurethane foam heat insulation material, the performance of the polyurethane foam is shown in Table 4.
Table 4:
Table 4 statistics indicate that, compared with comparative example, organic silicon surfactant provided by the invention liquefaction obtained is natural
Gas (LNG) heat preservation hard polyurethane foam has lower burning height and compared with high bond strength.
Test example 5:
Select commercially available organic silicon surfactantOrganosilicon L6900 is as comparative example 5, the conduct pair of embodiment 2
Ultralow temperature hard polyurethane polyureas urethane foams are prepared for according to group, specific implementation step is as follows:
(1) preparation of polyurethane foam composition
100 parts of combined polyether glycol, 2 parts of the organic silicon surfactant of embodiment 2,16 parts of foaming agent LBA, water 1.0
Part and 10 parts of fire retardant TCPP.
According to above-mentioned formula, each ingredient is added in stainless steel mixing kettle, it is small with the revolving speed stirring 1 of 500r/min at room temperature
When, blowing is up to polyurethane foam composition.
(2) preparation of polyurethane foam heat insulation material:
Polyurethane foam composition and isocyanates PM200 are used into spraying robot, according to the ratio of volume ratio 1: 1.0
Example preparation density is about 40kg/m3Polyurethane foam heat insulation material, the performance of the polyurethane foam is shown in Table 5.
Table 5:
Table 5 statistics indicate that, compared with comparative example, organic silicon surfactant provided by the invention liquefaction obtained is natural
Gas (LNG) heat preservation hard polyurethane foam has lower burning height and compared with high bond strength.
Test example 6:
Select commercially available organic silicon surfactantOrganosilicon L6900 is as comparative example 6, the conduct pair of embodiment 3
Ultralow temperature hard polyurethane polyureas urethane foams are prepared for according to group, specific implementation step is as follows:
(1) preparation of polyurethane foam composition
100 parts of combined polyether glycol, 5 parts of the organic silicon surfactant of embodiment 3,16 parts of foaming agent LBA, water 1.0
Part and 10 parts of fire retardant TCPP.
According to above-mentioned formula, each ingredient is added in stainless steel mixing kettle, it is small with the revolving speed stirring 1 of 500r/min at room temperature
When, blowing is up to polyurethane foam composition.
(2) preparation of polyurethane foam heat insulation material:
Polyurethane foam composition and isocyanates PM200 are used into spraying robot, according to the ratio of volume ratio 1: 1.0
Example preparation density is about 40kg/m3Polyurethane foam heat insulation material, the performance of the polyurethane foam is shown in Table 6.
Table 6:
Table 6 statistics indicate that, compared with comparative example, organic silicon surfactant provided by the invention liquefaction obtained is natural
Gas (LNG) heat preservation hard polyurethane foam has lower burning height and compared with high bond strength.
In addition, being also prepared for liquefied natural gas to other molecular formula silicone copolymer surfactants provided by the invention
(LNG) prepared by the silicone copolymer surfactants of heat preservation hard polyurethane foam, effect and Examples 1 to 3 preparation
Hard matter polyurethane foam performance it is consistent, be improved anti-flammability, improve adhesion strength effect.
In the case where meeting requirement and quality standard, adding the invention silicone copolymer surfactants can be with
The additive amount for significantly reducing fire retardant facilitates the linear dimension change rate for reducing hard polyurethane foam；It can subtract simultaneously
The usage amount of few physical blowing agent LBA, is effectively reduced product cost.
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 (6)
1. a kind of silicone copolymer surfactants, it is characterised in that: it is with following general formula: MDxD’yM；Wherein, M is selected from
(CH3)3SiO1/2、(CH3)2R’SiO1/2Any one of；D is (CH3)2SiO2/2；D ' is (CH3)2(R)SiO2/2,；X+y be 8~
30, y be 2~6；The R ' compound selected from the group below:
(1) at least one allyl polyethenoxy ether, general formula are as follows: CnH2n(C2H4O)a(C3H6O)bOH, weight average molecular weight 200-
700, it be 2~16, b is 2~16 that wherein n, which is 2~4, a, and in segment polyethylene oxide section and polypropylene oxide segments weight
Than for 60~100:0~40；
(2) at least one phenylacetylene base silane；
(3) molar ratio of phenylacetylene base silane and allyl polyethenoxy ether is 1:4~1:10.
2. a kind of silicone copolymer surfactants according to claim 1, it is characterised in that: the phenylacetylene base
Silane is tolans base silane, any one in three phenylacetylene base silanes or four phenylacetylene base silanes；
The structure of tolans base silane is as follows, in which: R1,R2For alkyl or aryl:
The structure of three phenylacetylene base silanes is as follows, in which: R be alkyl or aryl:
The structure of four phenylacetylene base silanes is as follows:
3. organic silicon surfactant described in claim 1 is in preparing liquefied natural gas heat preservation hard foamed poly urethane
Application.
4. a kind of polyurethane foam composition of liquefied natural gas heat preservation, it is characterised in that: in parts by weight, by with
Lower raw material mixes:
The viscosity of above-mentioned polyurethane foam composition is 3000~5000mPa.s (25 DEG C), and hydroxyl value is 250~350mgKOH/
G, moisture content weight content is less than 0.1%；
5. a kind of polyurethane foam composition of liquefied natural gas heat preservation according to claim 4, it is characterised in that:
The foaming agent is 1,1,1,3,3- pentafluoropropane, 1,1,1,3,3- 3-pentafluorobutane, chlorotrifluoropropylene, pentamethylene or just
Any one in pentane.
6. a kind of polyurethane foam composition of liquefied natural gas heat preservation according to claim 4, it is characterised in that:
The fire retardant is three (2- chloropropyl) phosphates, three (2- chloroethyl) phosphates, triethyl phosphate or methyl acid phosphate diformazan
Ester.
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| CN112250871A (en) * | 2020-10-26 | 2021-01-22 | 上海麦豪新材料科技有限公司 | Preparation method of alkynyl polyether modified organic silicon surfactant |
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