CN106432672A - All-water-blown rigid polyurethane foam material and production method thereof - Google Patents
All-water-blown rigid polyurethane foam material and production method thereof Download PDFInfo
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- CN106432672A CN106432672A CN201610826285.3A CN201610826285A CN106432672A CN 106432672 A CN106432672 A CN 106432672A CN 201610826285 A CN201610826285 A CN 201610826285A CN 106432672 A CN106432672 A CN 106432672A
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- water foamed
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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
- C08G18/54—Polycondensates of aldehydes
- C08G18/544—Polycondensates of aldehydes with nitrogen 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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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
- C08J9/125—Water, e.g. hydrated salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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 invention provides an all-water-blown rigid polyurethane foam material and a production method thereof. The material is prepared from isocyanate and an all-water blowing agent through mixing and foaming; the all-water foaming agent is prepared from inorganic hybrid amino resin polyol, an emulsifier, a composite catalyst, low-viscosity phosphate and water through mixing and impurity filtering; all the components of the all-water blowing agent are weighed in parts by weight, mixed and evenly stirred, impurities are filtered out, a filter cake, that is, the all-water blowing agent, is obtained; then isocyanate and the prepared all-water blowing agent are mixed in the weight ratio being (1-1.6):1 and foamed, and the all-water-blown rigid polyurethane foam material is prepared. Compared with like products, the material and the production method have obvious technical advantages and economic advantages, and a thermal-insulation material integrating environment friendliness, B1-grade flame retardance and waterproofness is provided for building energy saving.
Description
Technical field
The invention belongs to polyurethane material synthesis field, especially relates to the synthesis neck of full water foamed polyurethane rigid foam material
Domain.
Background technology
China is the big country of climate characteristic complexity, the such as the Northeast of severe cold, the River of summer hot cold,
This causes the energy consumption of China's building materials very big.Winter warming of northern area etc., energy consumption accounts for the 27.3% of national total energy consumption.
But the problem due to material, technology and technique, China's traditional architecture unit area heating energy consumption is weather conditions phase in the world
2-3 times of near developed country.Country promulgates《Long-term ad hoc planning in energy-conservation》Regulation：" 13. five " during new building
Strict implement energy conservation standard is wanted, while will progressively implement adiabatic heat-insulation transformation to existing building.65% energy-conservation mark is carried out comprehensively
Standard, 75% energy conservation standard is carried out in a line city.
At present China using heat insulating energy saving material mainly include following several：Foam type insulation material, composition silicate
Insulation material, heat-insulating calcium silicate product insulation material.
The foam type insulation material for using at home is mainly EPS insulation material；And polyurethane (PU) insulation material and EPS
Insulation material is compared, and heat conductivity is lower, and the heat insulation effect of the PU rigid foam of 50mm thickness is equivalent to 80-100mm thickness
EPS.Particularly when energy-conservation 65% is realized in north cold area, EPS seam leak, there is serious freeze thawing phenomenon, come off existing
As serious.
Ordinary rigid polyurethane foam plastics typically adopts low boiling hydrocarbon compound fluorochlorohydrocarbon (F11,141B etc.) conduct
Foaming agent is right, and discovered in recent years is the arch-criminal for destroying earth's ozone layer by such compound.HCFC (HCFC) class also has
There is certain ozone remove function and greenhouse effect is produced, so original polyurethane foam system must be substituted, therefore entirely
Water blown technology increasingly receives the favor of people.
And there are many deficiencies in common Water-Blown Rigid Polyurethane Foams：As system viscosity too large fluidity is poor,
Foam uneven and cause abscess thick, heat conductivity is bigger than normal, foams embrittlement etc..
Content of the invention
A kind of it is an object of the invention to provide full water foamed B1 level flame retardant inorganic hybrid polyurethane rigid foam material, while also public affairs
The manufacture method of the material is opened, the material and its manufacture method are compared with like product with obvious technical advantage and economy
Advantage, is that building energy conservation provides environmental protection, B1 level is fire-retardant, invent waterproof integrated insulation material.Can be in building field, oil
Widely use in the fields such as chemical field, freezer cold insulation, great economic benefit will be produced, while country is completed to execute covering spy
Rel agreement plan, reduces atmospheric warming effect, and protection atmospheric ozone layer has huge social benefit.
The invention provides a kind of full water foamed polyurethane rigid foam material, by after isocyanates and full water foamed dose of mixing
Brewed；Described full water foamed dose by inorganic hybridization amino resins polyhydric alcohol, emulsifying agent, composite catalyst, low viscosity phosphate ester
Miscellaneous prepared with filtering after water mixing.
Inorganic hybridization amino resins polyhydric alcohol used in the foaming agent of the present invention, does not contain low boiling hydrocarbon compound fluorine chlorine
Hydrocarbon and HCFC class compound, with full water foamed, do not damage the ozone layer, do not produce greenhouse effect；Also, due to inorganic hybridization
Amino resins polyhydric alcohol itself has very high anti-flammability, so the full water foamed polyurethane rigid foam material for being manufactured using which is corresponding
Just have very high anti-flammability.
Additionally, the present invention is entered to full water foamed B1 level flame melamine polyurethane composition polyethers using low viscosity phosphate ester
Row effectively dilutes, and it is too big to overcome full water foamed polyurethane composition polyethers viscosity, poor fluidity, foaming is uneven and cause abscess
Thick, heat conductivity is bigger than normal, the low defect of foams embrittlement, intensity.While providing the phosphorus source of phosphorus-nitrogen flame-retardant system, improve
The fire resistance of full water foamed polyurethane with melamine foamed materialss.
Further, in described full water foamed dose inorganic hybridization amino resins polyhydric alcohol be 60-65 weight portion, emulsifying agent be
1.5-3 weight portion, composite catalyst are 4-5 weight portion, low viscosity phosphate ester is 25-30 weight portion, water is 1.5-3 weight portion
Further, the weight ratio of the isocyanates and full water foamed dose be:1.
Further, the inorganic hybridization amino resins polyhydric alcohol is lower formula (I), (II), at least one of (III)：
In formula, M be-B (OH)-, one of-Sb (OH)-or-Mo (=O) 2-, R is that monohydric alcohol or polyhydric alcohol lose a hydroxyl
The substituent group of base, R1 loses the substituent group of a hydroxyl for monohydric alcohol.
Further, the emulsifying agent is for hard bubbling silicone oil, such as commercially available AK8805, SD624, and SD622 etc. hard bubbles silicone oil
In one or two combination.
Further, described composite catalyst is：Potassium acetate, five methyl diethylentriamine, tri- (diformazan of 1,3,5-
Aminocarbonyl propyl) Hexahydrotriazine, trimethyl-N-2 hydroxypropyl caproic acid, triethylenediamine, some in dibutyl tin laurate
Kind.
Further, described low viscosity phosphate ester, is tricresyl phosphate (the chloro- 2- propyl group of 1-) ester, tricresyl phosphate (2,3- dichloros
Propyl group) one or two combinations in ester.
The present invention also provides another kind of full water foamed polyurethane rigid foam material, after isocyanates and full water foamed dose of mixing
Foaming is obtained；After described full water foamed dose is mixed by Phos hydridization amino resins polyhydric alcohol, emulsifying agent, composite catalyst and water
Filter is miscellaneous to be obtained, and is primary raw material, to directly obtain phosphorus-nitrogen anti-flammability system to provide phosphorus and nitrogen using phospha amino resins polyhydric alcohol
Element.
The present invention also provides a kind of full water foamed polyurethane rigid foam material ground manufacture method, comprises the following steps：
S1, is mixed and stirred for after above-mentioned full water foamed dose of each component is weighed by weight uniformly, filtering out impurity, obtaining
To filter cake, full water foamed dose is obtained final product；
S2, full water foamed dose by isocyanates and S1 preparation is (1～1.6) according to weight ratio:After 1 mixing, carry out sending out
Bubble operation, obtains full water foamed polyurethane rigid foam material.
Further, the foaming operation in S2 can be that flush coater spray coating foaming, or casting machine pouring foaming become
Shell, can also be on panel machine and is foamed into sheet material.The rigid foam material for being manufactured using said method, its oxygen index (OI) is more than 30%.
Specific embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Specific embodiment
Embodiment 1：The preparation of full water foamed B1 level flame melamine polyurethane coating rigid foam material
S1：Following materials being added separately in mixing kettle, start stirring, is sufficiently stirred for disperseing 2 hours, filters out original
The micro mechanical admixture that material strip comes, obtains full water foamed dose, inspires the time：The 3-5 second.
S2：Prepared by S1 full water foamed dose and isocyanate polymeric MDI, compares 1 according to weight:1 mixing, is sprayed with flush coater
Foaming is applied, obtains full water foamed polyurethane rigid foam material：Full water foamed B1 level flame melamine polyurethane coating rigid foam material.Warp
Detection, density：35Kg/m3；Oxygen index (OI)：30.7；Reach fire retardant B1 level.
Embodiment 2：The continuous preparation of plates of full water foamed B1 level flame melamine hard polyurethane foam
S1：Following materials being added separately in mixing kettle, start stirring, is sufficiently stirred for disperseing 2 hours, filters out original
The micro mechanical admixture that material strip comes, obtains full water foamed dose.
S2：By S1 prepare full water foamed dose with isocyanate polymeric MDI, compare 1 according to weight:1.6 mixing, in sheet material
Sheet material is foamed on machine, obtains full water foamed polyurethane rigid foam material：Full water foamed B1 level flame melamine hard polyurethane foam is even
Continuous sheet material.After testing, its density：42Kg/m3；Oxygen index (OI)：31.6；Reach fire retardant B1 level.
Embodiment 3：The preparation of full water foamed cast B1 level flame melamine hard polyurethane foam cold storage plate
S1：Following materials being added separately in mixing kettle, start stirring, is sufficiently stirred for disperseing 2 hours, filters out original
The micro mechanical admixture that material strip comes, obtains full water foamed dose.
S2：Above-mentioned full water foamed dose is compared 1 with isocyanate polymeric MDI according to weight:1.5 mixing, pour on panel machine
Note is foamed into freezer sheet material.After testing, its density：41Kg/m3；Oxygen index (OI)：32.2；Reach fire retardant B1 level.
Embodiment 4：The preparation of full water foamed cast B1 level flame melamine hard polyurethane foam shell
S1：Following materials being added separately in mixing kettle, start stirring, is sufficiently stirred for disperseing 2 hours, filters out original
The micro mechanical admixture that material strip comes, obtains full water foamed cast B1 level flame melamine polyurethane shell material combined polyether.
S2：Above-mentioned full water foamed dose is compared 1 with isocyanate polymeric MDI according to weight:1.5 mixing, with casting machine, pour into a mould
It is foamed into shell.After testing, its density：38Kg/m3；Oxygen index (OI)：31.3；Reach fire retardant B1 level.
The trimerization of the Inorganic Boron hydridization for representing for following formula for high temperature resistant melmac polyhydric alcohol in above-described embodiment
Melamine resin polyol blends.Its preparation method be with hexakis(hydroxymethyl)melamine as raw material, in acid condition with methanol
There is etherification reaction Deng monohydric alcohol, then add the inorganic salt solution of the boron such as borate solution to carry out hydridization in neutral conditions anti-
Should, the high temperature resistant melmac polyhydric alcohol finally by ester exchange is carried out between ethylene glycol and methanol, needed for obtaining.
In other embodiments, boron can also be with other inorganic elementss hydridization such as antimony or molybdenum.Similar is inorganic miscellaneous
Change melmac polyol blends and its specific preparation method may be referred to Application No. 201610736810.2
Application for a patent for invention.
Claims (10)
1. a kind of full water foamed polyurethane rigid foam material, it is characterised in that by foaming after isocyanates and full water foamed dose of mixing
It is obtained；Described full water foamed dose by inorganic hybridization amino resins polyhydric alcohol, emulsifying agent, composite catalyst, low viscosity phosphate ester and
Miscellaneous being obtained is filtered after water mixing.
2. a kind of full water foamed polyurethane rigid foam material according to claim 1, it is characterised in that described full water foamed dose
Middle inorganic hybridization amino resins polyhydric alcohol is 60-65 weight portion, emulsifying agent is 1.5-3 weight portion, composite catalyst is 4-5 weight
Part, low viscosity phosphate ester are 25-30 weight portion, water is 1.5-3 weight portion
3. a kind of full water foamed polyurethane rigid foam material according to claim 1 and 2, it is characterised in that the Carbimide.
The weight ratio of ester and full water foamed dose is (1～1.6):1.
4. a kind of full water foamed polyurethane rigid foam material according to one of claims 1 to 3, it is characterised in that the nothing
Machine hydridization amino resins polyhydric alcohol is lower formula (I), (II), at least one of (III)：
In formula, M be-B (OH)-,-Sb (OH)-or-Mo (=O)2One of-, R is that monohydric alcohol or polyhydric alcohol lose taking for a hydroxyl
Dai Ji, R1The substituent group of a hydroxyl is lost for monohydric alcohol.
5. a kind of full water foamed polyurethane rigid foam material according to one of claims 1 to 3, it is characterised in that the breast
Agent is the silicone oil that hard bubbles.
6. a kind of full water foamed polyurethane rigid foam material according to one of claims 1 to 3, it is characterised in that described
Composite catalyst is：Potassium acetate, five methyl diethylentriamine, 1,3,5- tri- (dimethylamino-propyl) Hexahydrotriazine, trimethyl-
Several in N-2 hydroxypropyl caproic acid, triethylenediamine, dibutyl tin laurate.
7. a kind of full water foamed polyurethane rigid foam material according to one of claims 1 to 3, it is characterised in that described
Low viscosity phosphate ester is tricresyl phosphate (the chloro- 2- propyl group of 1-) ester, one or two groups in tricresyl phosphate (2,3- bis- chloropropyl) ester
Close.
8. a kind of full water foamed polyurethane rigid foam material, it is characterised in that by foaming after isocyanates and full water foamed dose of mixing
It is obtained；Described full water foamed dose miscellaneous by filtering after the mixing of Phos hydridization amino resins polyhydric alcohol, emulsifying agent, composite catalyst and water
It is obtained.
9. a kind of full water foamed polyurethane rigid foam material ground manufacture method, comprises the following steps：
S1, is mixed and stirred for uniform, filtration after full water foamed dose described in claim 1-8 of each component is weighed by weight
Go out impurity, obtain filter cake, i.e., described full water foamed dose；
S2, full water foamed dose by isocyanates and S1 preparation is (1～1.6) according to weight ratio:After 1 mixing, foaming behaviour is carried out
Make, obtain the full water foamed polyurethane rigid foam material.
10. full water foamed polyurethane rigid foam material ground according to claim 9 manufacture method, it is characterised in that described
Steeping operation is：Flush coater spray coating foaming, casting machine pouring foaming become on shell or panel machine to be foamed into sheet material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610806778 | 2016-09-07 | ||
| CN2016108067780 | 2016-09-07 |
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| Publication Number | Publication Date |
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| CN106432672A true CN106432672A (en) | 2017-02-22 |
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| CN201610826285.3A Pending CN106432672A (en) | 2016-09-07 | 2016-09-18 | All-water-blown rigid polyurethane foam material and production method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018023986A1 (en) * | 2016-08-01 | 2018-02-08 | 常州聚博节能科技有限公司 | Water-blown rigid inorganic hybrid melamine polyurethane foam material and preparation method therefor |
| CN108239254A (en) * | 2018-02-12 | 2018-07-03 | 吴艳飞 | Full water foamed B1 grades of resistance combustion polyurethane foam thermal insulation material and preparation method thereof |
| CN113354794A (en) * | 2021-05-25 | 2021-09-07 | 苏州恒利峰节能建材科技有限公司 | Full-water-blown flame-retardant polyurethane and foamed ceramic composite thermal insulation material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987484A (en) * | 2015-05-29 | 2015-10-21 | 张家港迪蒙德节能科技有限公司 | Inorganic material hybrid hard melamine polyurethane foam heat insulation material, preparation method thereof and combined polyether used therein |
| CN104987482A (en) * | 2015-08-06 | 2015-10-21 | 深圳市桑得特实业发展有限公司 | Full-water type flame-resistant rigid polyurethane foam, composite heat insulation board and preparation method therefor |
| CN106243302A (en) * | 2016-08-01 | 2016-12-21 | 常州聚博节能科技有限公司 | Water blown inorganic hybridization polyurethane with melamine rigid foam material and manufacture method thereof |
-
2016
- 2016-09-18 CN CN201610826285.3A patent/CN106432672A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987484A (en) * | 2015-05-29 | 2015-10-21 | 张家港迪蒙德节能科技有限公司 | Inorganic material hybrid hard melamine polyurethane foam heat insulation material, preparation method thereof and combined polyether used therein |
| CN104987482A (en) * | 2015-08-06 | 2015-10-21 | 深圳市桑得特实业发展有限公司 | Full-water type flame-resistant rigid polyurethane foam, composite heat insulation board and preparation method therefor |
| CN106243302A (en) * | 2016-08-01 | 2016-12-21 | 常州聚博节能科技有限公司 | Water blown inorganic hybridization polyurethane with melamine rigid foam material and manufacture method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018023986A1 (en) * | 2016-08-01 | 2018-02-08 | 常州聚博节能科技有限公司 | Water-blown rigid inorganic hybrid melamine polyurethane foam material and preparation method therefor |
| CN108239254A (en) * | 2018-02-12 | 2018-07-03 | 吴艳飞 | Full water foamed B1 grades of resistance combustion polyurethane foam thermal insulation material and preparation method thereof |
| CN113354794A (en) * | 2021-05-25 | 2021-09-07 | 苏州恒利峰节能建材科技有限公司 | Full-water-blown flame-retardant polyurethane and foamed ceramic composite thermal insulation material and preparation method thereof |
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