CN104479093A - Preparation method of flame-retardant rigid polyurethane foam - Google Patents
Preparation method of flame-retardant rigid polyurethane foam Download PDFInfo
- Publication number
- CN104479093A CN104479093A CN201410807618.9A CN201410807618A CN104479093A CN 104479093 A CN104479093 A CN 104479093A CN 201410807618 A CN201410807618 A CN 201410807618A CN 104479093 A CN104479093 A CN 104479093A
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- CN
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- Prior art keywords
- foam
- polyurethane foam
- rigid polyurethane
- flame
- foaming
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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
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
-
- 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
- C08G18/08—Processes
- C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
- C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
- C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
-
- 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
-
- 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 invention discloses a preparation method of flame-retardant rigid polyurethane foam. A new flame retardant OH-R-OH (the R structure contains phosphorus) is used for preparing the rigid polyurethane foam (polyether 4110, PM200); the system temperature is adjusted to 18 DEG C after polyhydroxy polyether, a foam stabilizer, a catalyst, a foaming agent and a toughening agent are weighed in proportion and evenly mixed, then the mixture is mixed with a proper amount of polyisocyanate at the high speed, the mixture is injected into a mold for foaming when conditions that bubbles are produced and bubble bodies turn white are observed, and rigid polyurethane foam plastic is obtained through expansion fixation, demolding and post-curing. When the rigid polyurethane foam is prepared with the method, effects caused by selection and parts of raw materials on the molding process and performance of the rigid polyurethane foam are great, the effect caused by selection of polyhydric alcohol on the performance of the rigid polyurethane foam is greater, and process technologies as well as research and development of new products are improved.
Description
Technical field
The invention discloses the preparation method that a kind of flame-retardant polyurethane hard bubbles.
Background technology
For improving the flame retardant resistance of porous plastics, by adding fire retardant, fire position even can being made from putting out with retarded combustion, resistance cigarette, the polyvalent alcohol (i.e. reactive flame retardant) containing ignition-proof element also can be adopted to be foam raw material.Fire retardant must have function in following a kind of Huo Shu: can become non-combustible material in kindling temperature or close to thermal endothermic decomposition under kindling temperature; Can react with foam combustion product and generate nonflammable material; Decomposable asymmetric choice net goes out to stop the material of foam free-radical oxidn reaction.
In hard polyurethane foam, phosphonium flame retardant mainly plays a role at condensed phase, the inflammable gas that decomposites when phosphide can consume porous plastics burning, makes it change into nonflammable carbide, and in foams, phosphorus content reaches about 1.5% and can obtain preferably flame retardant effect.The fire retardant of polyurethane hard foam, based on liquid combustion inhibitor, adds fire retardant and has delayed the thermolysis of foam, initial decomposition temperature is improved.Solid-state fire retardant adds in liquid raw material and easily precipitates, generally before foaming or foaming time add, solid-state fire retardant adds can make material viscosity increase.
Summary of the invention
The present invention relates to the preparation method that a kind of flame-retardant polyurethane hard bubbles, adopt a kind of new fire retardant OH-R-OH(R structure phosphorous), use it for and prepare hard polyurethane foam (polyethers 4110, PM200); Take after multi-hydroxy polyether, foam stabilizer, catalyzer, whipping agent and toughner mix by proportioning and system temperature is adjusted to 18 DEG C, then high-speed stirring mixes together with appropriate polymeric polyisocyanate, inject mould when observation has bubble to send, foam turns white to foam, through swollen fixed, demoulding and after fixing, both obtained polyurethane rigid foam plastic, the method adopts following steps:
(1) selection of polyethers;
Polyether glycol and polyester polyol are two kinds of main raw materials of synthesis of polyurethane rigid foam plastic, and they are band degrees of branching, lower molecular weight and the higher resin of viscosity, polyvalent alcohol is used in rigid foam, general requirement is molecular weight less than 1300, and hydroxyl value is less than 700, and functionality is between 3 ~ 8;
(2) catalyzer and consumption thereof are selected;
In rigid urethane foam moulding process, catalyzer is divided into tertiary amine catalyst and organic tin catalyzer, different ratios between the two and consumption directly will affect cream time, rise time and sticky time and quality product, the Main Function of organotin to produce tiny and uniform microvoid structure, promotes rapid gelling or foam sclerosis, and tertiary amine can initiated polymerization rapidly, and gelation time and the set time of foam can be extended, it to transfer reaction and foamable reaction all effective;
(3) impact of stablizer;
Silicone oil (dimethyl siloxane) is a kind of tensio-active agent, also be a kind of foaming stabiliser, it is a kind of silicone macromolecule compound: first make several material evenly mix mutually, as the emulsifying agent of hydrophilic polyester and hydrophobic isocyanic ester, fluorocarbon, next is stable foaming, reduces foam surface tension force in foaming process, and when preventing gelling, micropore merges, serve the effect controlling micropore size, its add-on is 0.1% ~ 0.2%.
The density of described hard polyurethane foams affects by foaming agent consumption to a great extent, and along with the increase of foaming agent consumption, its density constantly reduces.
Described fire retardant OH-R-OH(R structure is phosphorous) structure is for the preparation of polyethers.
The positively effect that the present invention has is:
When the present invention prepares hard polyurethane foams, the selection of raw material and number on the moulding process of hard polyurethane foams and the impact of performance very big, the selection of this wherein polyvalent alcohol is comparatively large for the performance impact of hard polyurethane foams, improves the research and development of Technology and product innovation.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, and be not used in restriction invention.
The preparation method that a kind of flame-retardant polyurethane hard bubbles.Adopt a kind of new fire retardant OH-R-OH(R structure phosphorous), use it for and prepare hard polyurethane foam (polyethers 4110, PM200); Take after multi-hydroxy polyether, foam stabilizer, catalyzer, whipping agent and toughner mix by proportioning and system temperature is adjusted to 18 DEG C, then high-speed stirring mixes together with appropriate polymeric polyisocyanate, inject mould when observation has bubble to send, foam turns white to foam, through swollen fixed, demoulding and after fixing, both obtained polyurethane rigid foam plastic, the method adopts following steps:
(1) selection of polyethers;
Polyether glycol and polyester polyol are two kinds of main raw materials of synthesis of polyurethane rigid foam plastic, and they are band degrees of branching, lower molecular weight and the higher resin of viscosity, polyvalent alcohol is used in rigid foam, general requirement is molecular weight less than 1300, and hydroxyl value is less than 700, and functionality is between 3 ~ 8;
(2) catalyzer and consumption thereof are selected;
In rigid urethane foam moulding process, catalyzer is divided into tertiary amine catalyst and organic tin catalyzer, different ratios between the two and consumption directly will affect cream time, rise time and sticky time and quality product, the Main Function of organotin to produce tiny and uniform microvoid structure, promotes rapid gelling or foam sclerosis, and tertiary amine can initiated polymerization rapidly, and gelation time and the set time of foam can be extended, it to transfer reaction and foamable reaction all effective;
(3) impact of stablizer;
Silicone oil (dimethyl siloxane) is a kind of tensio-active agent, also be a kind of foaming stabiliser, it is a kind of silicone macromolecule compound: first make several material evenly mix mutually, as the emulsifying agent of hydrophilic polyester and hydrophobic isocyanic ester, fluorocarbon, next is stable foaming, reduces foam surface tension force in foaming process, and when preventing gelling, micropore merges, serve the effect controlling micropore size, its add-on is 0.1% ~ 0.2%.
The density of hard polyurethane foams affects by foaming agent consumption to a great extent, and along with the increase of foaming agent consumption, its density constantly reduces.
Fire retardant OH-R-OH(R structure is phosphorous) structure is for the preparation of polyethers.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. a flame-retardant polyurethane preparation method of hard bubbling, is characterized in that: adopt a kind of new fire retardant OH-R-OH(R structure phosphorous), use it for and prepare hard polyurethane foam (polyethers 4110, PM200); Take after multi-hydroxy polyether, foam stabilizer, catalyzer, whipping agent and toughner mix by proportioning and system temperature is adjusted to 18 DEG C, then high-speed stirring mixes together with appropriate polymeric polyisocyanate, inject mould when observation has bubble to send, foam turns white to foam, through swollen fixed, demoulding and after fixing, both obtained polyurethane rigid foam plastic, the method adopts following steps: the selection of (1) polyethers; Polyether glycol and polyester polyol are two kinds of main raw materials of synthesis of polyurethane rigid foam plastic, and they are band degrees of branching, lower molecular weight and the higher resin of viscosity, polyvalent alcohol is used in rigid foam, general requirement is molecular weight less than 1300, and hydroxyl value is less than 700, and functionality is between 3 ~ 8; (2) catalyzer and consumption thereof are selected; In rigid urethane foam moulding process, catalyzer is divided into tertiary amine catalyst and organic tin catalyzer, different ratios between the two and consumption directly will affect cream time, rise time and sticky time and quality product, the Main Function of organotin to produce tiny and uniform microvoid structure, promotes rapid gelling or foam sclerosis, and tertiary amine can initiated polymerization rapidly, and gelation time and the set time of foam can be extended, it to transfer reaction and foamable reaction all effective;
The impact of stablizer; Silicone oil (dimethyl siloxane) is a kind of tensio-active agent, also be a kind of foaming stabiliser, it is a kind of silicone macromolecule compound: first make several material evenly mix mutually, as the emulsifying agent of hydrophilic polyester and hydrophobic isocyanic ester, fluorocarbon, next is stable foaming, reduces foam surface tension force in foaming process, and when preventing gelling, micropore merges, serve the effect controlling micropore size, its add-on is 0.1% ~ 0.2%.
2. a kind of flame-retardant polyurethane preparation method of hard bubbling according to claim 1, it is characterized in that, the density of described hard polyurethane foams affects by foaming agent consumption to a great extent, and along with the increase of foaming agent consumption, its density constantly reduces.
3. a kind of flame-retardant polyurethane preparation method of hard bubbling according to claim 1, it is characterized in that, described fire retardant OH-R-OH(R structure is phosphorous) structure is for the preparation of polyethers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410807618.9A CN104479093A (en) | 2014-12-23 | 2014-12-23 | Preparation method of flame-retardant rigid polyurethane foam |
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|---|---|---|---|
| CN201410807618.9A CN104479093A (en) | 2014-12-23 | 2014-12-23 | Preparation method of flame-retardant rigid polyurethane foam |
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| CN104479093A true CN104479093A (en) | 2015-04-01 |
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| CN201410807618.9A Pending CN104479093A (en) | 2014-12-23 | 2014-12-23 | Preparation method of flame-retardant rigid polyurethane foam |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117600A (en) * | 2016-07-01 | 2016-11-16 | 中国科学院山西煤炭化学研究所 | Phosphonium flame retardant and synthetic method and the application in hard polyurethane foam |
| CN109293878A (en) * | 2018-09-12 | 2019-02-01 | 北京理工大学 | A kind of preparation method of high insulating polyimide hard bubble bead |
| CN109364107A (en) * | 2018-11-30 | 2019-02-22 | 奚正华 | A kind of absorbefacient emplastrum of releiving of aching of spontaneous heating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585153A (en) * | 2012-03-07 | 2012-07-18 | 厦门大学 | Halogen-free and flame-retardant hard polyurethane foam plastic and preparation method thereof |
| CN103012737A (en) * | 2013-01-10 | 2013-04-03 | 江苏斯泰达新能源科技发展有限公司 | 100% water-base foamed polyurethane foam and preparation method thereof |
| CN104045806A (en) * | 2013-03-13 | 2014-09-17 | 拜耳材料科技(中国)有限公司 | Polyurethane composition for preparing polyurethane composite material |
-
2014
- 2014-12-23 CN CN201410807618.9A patent/CN104479093A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585153A (en) * | 2012-03-07 | 2012-07-18 | 厦门大学 | Halogen-free and flame-retardant hard polyurethane foam plastic and preparation method thereof |
| CN103012737A (en) * | 2013-01-10 | 2013-04-03 | 江苏斯泰达新能源科技发展有限公司 | 100% water-base foamed polyurethane foam and preparation method thereof |
| CN104045806A (en) * | 2013-03-13 | 2014-09-17 | 拜耳材料科技(中国)有限公司 | Polyurethane composition for preparing polyurethane composite material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117600A (en) * | 2016-07-01 | 2016-11-16 | 中国科学院山西煤炭化学研究所 | Phosphonium flame retardant and synthetic method and the application in hard polyurethane foam |
| CN109293878A (en) * | 2018-09-12 | 2019-02-01 | 北京理工大学 | A kind of preparation method of high insulating polyimide hard bubble bead |
| CN109293878B (en) * | 2018-09-12 | 2020-11-06 | 北京理工大学 | Preparation method of high-insulation polyurethane hard bubble small ball |
| CN109364107A (en) * | 2018-11-30 | 2019-02-22 | 奚正华 | A kind of absorbefacient emplastrum of releiving of aching of spontaneous heating |
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Application publication date: 20150401 |