CN110283351A - A kind of flame retarded rigid polyurethane foams plastics and preparation method thereof - Google Patents
A kind of flame retarded rigid polyurethane foams plastics and preparation method thereof Download PDFInfo
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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
- C08G18/08—Processes
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
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- 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
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- 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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- 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
- C08J9/0066—Use of inorganic compounding ingredients
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- 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
- C08J9/141—Hydrocarbons
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
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- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/00—Properties
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
A kind of flame retarded rigid polyurethane foams plastics and preparation method thereof, belong to fire proofing technical field, solve the low technical problem of existing resistance combustion polyurethane foam poor compatibility, flame retarding efficiency.The raw material of resistance combustion polyurethane foam forms and its mass fraction are as follows: 100 parts of polyether polyol, 2~5 parts of catalyst, 5~10 parts of crosslinking agent, 5~20 parts of foaming agent, 100~120 parts of poly methylene poly phenyl poly isocyanate, 40 parts of fire retardant.Polyether polyol, fire retardant, catalyst and auxiliary agent are mixed and are used as component A, poly methylene poly phenyl poly isocyanate is as component B, raw material in component B is added in the uniformly mixed component A of raw material and is quickly stirred, natural foaming post curing reaction obtains resistance combustion polyurethane foam.Preparation process of the present invention is simple, and the used time is short, and the foam of preparation had not only remained the good thermal insulation property of polyurethane foamed material, but also is compounded with the good flame retardant property of ammonium polyphosphate, magnesium hydroxide, and low manufacture cost has a wide range of application.
Description
Technical field
The invention belongs to fire proofing technical fields, and in particular to be a kind of flame retarded rigid polyurethane foams plastics and its
Preparation method.
Background technique
Polyurethane foam (PUF) is a kind of emerging high-molecular organic material, has good thermal insulation, corrosion resistance and guarantor
Warm nature energy is widely applied in fields such as building, automobile, petrochemical pipe and storage heat preservations.China's urban architecture fire
It takes place frequently, not only threatens people's life and property safety, also generate a large amount of harmful vapors, pollute environment.Currently, new in construction material
Type thermal insulation building material emerges one after another, polyurethane foam plastics with its excellent thermal and insulating performance and unique lightweight,
The features such as low water absorption, is widely used in building energy saving field.But due to the poor fire of polyurethane foam product, cost
Height makes its application be restricted.
For the flame retardant property or grade for so that product is reached required, traditional technology is usually used to be added into material system
Add halogen-containing fire retardant matter, such as addition such as deca-BDE, Brominated Polystyrene, pentabromotoluene or six into system material
Relatively high or relatively high containing the halogen quantity organic chemicals of the brominated amount such as bromine cyclododecane, these halogen-containing fire retardant matters
Although anti-flammability is preferable, its usage amount is bigger, when high temperature or burning can generate difficult to degrade harmful substance pollution environment,
Influence the mankind and animal health.
Ammonium polyphosphate (APP) is one of the important component of expansion type flame retardant (IFR), has acid source and gas source dual
Function has many advantages, such as that phosphorus content is high, nitrogen content is more, thermal stability is good, is bordering on neutrality, is the heat in flame-retarded technology research field
One of point.Magnesium hydroxide (MH) itself have the function of it is fire-retardant, eliminate smoke, filling three, because its is non-volatile, nontoxic, but can with it is a variety of
Fire retardant generates cooperative flame retardant effect, is a kind of emerging environmental protection inorganic fire retardant.But the two is still deposited in practical applications
And the problems such as polymer compatibility is poor, flame retarding efficiency is limited.
Therefore, the rigid polyurethane foam that a kind of energy-saving heat preserving performance is good, fire safety performance is high is developed, to plastics
Preparation technical field has realistic meaning and application value.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of flame retarded rigid polyurethane foams plastics and its
Preparation method.
Design concept of the invention are as follows: different fire retardants, fire retardant mechanism is different, thus by being used in compounding, often
Good synergistic effect can be generated, significantly more flame retardant effect is obtained, improves the security performance of product.In this ammonium polyphosphate
(APP) it decomposes at high temperature reaction, the phosphoric acid of generation is stronger dehydrating agent, the dehydration carbonization of organic matter can be promoted,
Magnesium hydroxide (MH) is thermally decomposed into magnesia and vapor simultaneously, and with the raising of pyrolysis temperature, both reaction process
Constantly carrying out always, accelerating into the progress of charcoal reaction, make the layer of charcoal outer surface of fire-retardant PU formed one layer it is fine and close by P, O and
The magnesium phosphate class compound protective layer of Mg element composition, increases the compactness of surface layer of charcoal, with starvation and heat.APP
As gas source, incombustible gas is generated, fuel gas and oxygen concentration have been watered down, plays the role of slowing down burning.
The present invention is achieved by the following technical programs.
A kind of flame retarded rigid polyurethane foams plastics, the raw material composition and its mass fraction of the resistance combustion polyurethane foam
Are as follows: 100 parts of polyether polyol, 2~5 parts of catalyst, 5~10 parts of crosslinking agent, 5~20 parts of foaming agent, polymethylene polyphenyl is more
100~120 parts of isocyanates, 40 parts of fire retardant.
A kind of preparation method of flame retarded rigid polyurethane foams plastics, comprising the following steps:
S1, raw material is weighed respectively according to the raw material composition and its mass fraction of resistance combustion polyurethane foam, wherein flame retardant polyurethane steeps
The raw material of foam forms and its mass fraction is 100 parts of polyether polyol, and 2~5 parts of catalyst, 5~10 parts of crosslinking agent, foaming agent 5
~20 parts, 100~120 parts of poly methylene poly phenyl poly isocyanate, 40 parts of fire retardant；
S2, polyether polyol weighed in step S1, catalyst, crosslinking agent, foaming agent and fire retardant are mixed as component
The raw material of component A is stirred 3~5min until raw material is uniformly mixed with electric blender by A；
S3, it takes poly methylene poly phenyl poly isocyanate as component B for what is claimed in step S1, component B is rapidly joined and is filled
In the beaker of component A, while 10s is quickly stirred to mixed material presentation white using electric blender；
S4, foaming: mixture made from step S3 is quickly poured into natural foaming in ready mold；
S5, post-processing: product is cured to 5h in 90 DEG C of baking oven can be obtained flame retarded rigid polyurethane foams plastics.
Further, in the step S1, the catalyst is dibutyl tin dilaurate, and crosslinking agent is three ethyl alcohol
Amine, foaming agent are pentane, and fire retardant is ammonium polyphosphate and magnesium hydroxide, and ammonium polyphosphate is 20~30 parts, magnesium hydroxide 10
~20 parts.
Age resister, smog inhibitor, pigment etc. can be also added as needed in those of ordinary skill in the art.
Compared with prior art, the invention has the benefit that
1, the method for the present invention utilizes the synergistic action effect of fire retardant, makes ammonium polyphosphate and magnesium hydroxide cooperative flame retardant.Polyphosphoric acid
Ammonium will form the acid film of fixedness under the high temperature conditions, and the magnesia formed after can burning with magnesium hydroxide is bonded in one
Rise, thus accelerate hard bubble at charcoal, layer of charcoal delays the transmitting of oxygen and heat, plays flame retardant effect.
2, ammonium polyphosphate burns as gas source and generates incombustible CO in the method for the present invention2、NH3Equal gases, water down
Fuel gas and oxygen concentration play the role of slowing down burning；It vapor that magnesium hydroxide is thermally decomposed to generate while also functioning to
The effect of cooling.
3, the method for the present invention preparation process is simple, and the used time is short, and it is good that the foam of preparation had both remained polyurethane foamed material
Thermal insulation property, and be compounded with the good flame retardant property of ammonium polyphosphate, magnesium hydroxide, and low manufacture cost, have a wide range of application.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
Embodiment one
By 100 parts of polyether polyol, 3 parts of dibutyl tin dilaurates, 7 parts of triethanolamines, 10 parts of pentanes, 30 parts of ammonium polyphosphate
It is proportionally added into the plastic beaker of 600mL with 10 parts of magnesium hydroxides, it is equal to raw material mixing to stir 3~5min with electric blender
It is even, then 100 parts of poly methylene poly phenyl poly isocyanates (PAPI) are rapidly joined in beaker, while using electric blender
Quickly white is presented to mixed material in stirring 10s, is then quickly poured into obtained mixed material in ready mold certainly
So foaming, can be obtained flame retardant type PUF.After flame retarded rigid polyurethane foams plastics prepare, it is put into 90 DEG C of baking ovens and cures 5h
After be tested for the property.
Embodiment two
By 100 parts of polyether polyol, 3 parts of dibutyl tin dilaurates, 7 parts of triethanolamines, 10 parts of pentanes, 20 parts of ammonium polyphosphate
It is proportionally added into the plastic beaker of 600mL with 20 parts of magnesium hydroxides, stirs 3~5min to uniform, then with electric blender
100 parts of poly methylene poly phenyl poly isocyanates (PAPI) are rapidly joined in beaker, while quickly being stirred using electric blender
10s is mixed to whitening, obtained mixture is then quickly poured into natural foaming in ready mold, flame retardant type can be obtained
PUF.After flame retarded rigid polyurethane foams plastics prepare, it is put into after curing 5h in 90 DEG C of baking ovens and is tested for the property.
Comparative example
100 parts of polyether polyol, 3 parts of dibutyl tin dilaurates, 7 parts of triethanolamines, 10 parts of pentanes are proportionally added into
In the plastic beaker of 600mL, 3~5min is stirred to uniform, then by 100 parts of polymethylene polyphenyl polyisocyanates with electric blender
Cyanate (PAPI) rapidly joins in beaker, while using electric blender quickly stirring 10s to whitening, then will be obtained
Mixture is quickly poured into natural foaming in ready mold, obtains PUF.After foam prepares, it is put into 90 DEG C of baking ovens and cures
It is tested for the property after 5h.
Rigid polyurethane foam made from embodiment one, embodiment two and comparative example is tested for the property, wherein
By flame retardant rating by HB, the standard that V-2, V-1 are incremented by step by step to V-0 is detected for flame retardant rating test, the results are shown in Table 1:
1 the performance test results of table
Good, the flame retardant rating according to the flame retarded rigid polyurethane foams plastic flame performance produced by the present invention of data among the above
Height has broad application prospects.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
It is familiar with those skilled in the art in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (3)
1. a kind of flame retarded rigid polyurethane foams plastics, it is characterised in that: the raw material of the resistance combustion polyurethane foam form and its
Mass fraction are as follows: 100 parts of polyether polyol, 2~5 parts of catalyst, 5~10 parts of crosslinking agent, 5~20 parts of foaming agent, polymethylene
100~120 parts of polyphenyl polyisocyanate, 40 parts of fire retardant.
2. a kind of preparation method of flame retarded rigid polyurethane foams plastics as described in claim 1, it is characterised in that including with
Lower step:
S1, raw material is weighed respectively according to the raw material composition and its mass fraction of resistance combustion polyurethane foam, wherein flame retardant polyurethane steeps
The raw material of foam forms and its mass fraction is 100 parts of polyether polyol, and 2~5 parts of catalyst, 5~10 parts of crosslinking agent, foaming agent 5
~20 parts, 100~120 parts of poly methylene poly phenyl poly isocyanate, 40 parts of fire retardant；
S2, polyether polyol weighed in step S1, catalyst, crosslinking agent, foaming agent and fire retardant are mixed as component
The raw material of component A is stirred 3~5min until raw material is uniformly mixed with electric blender by A；
S3, it takes poly methylene poly phenyl poly isocyanate as component B for what is claimed in step S1, component B is rapidly joined and is filled
In the beaker of component A, while 10s is quickly stirred to mixed material presentation white using electric blender；
S4, foaming: mixture made from step S3 is quickly poured into natural foaming in ready mold；
S5, post-processing: product is cured to 5h in 90 DEG C of baking oven can be obtained flame retarded rigid polyurethane foams plastics.
3. a kind of preparation method of flame retarded rigid polyurethane foams plastics according to claim 1, it is characterised in that: in institute
It states in step S1, the catalyst is dibutyl tin dilaurate, and crosslinking agent is triethanolamine, and foaming agent is pentane, fire-retardant
Agent is ammonium polyphosphate and magnesium hydroxide, and ammonium polyphosphate is 20~30 parts, and magnesium hydroxide is 10~20 parts.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910348766.1A CN110283351A (en) | 2019-04-28 | 2019-04-28 | A kind of flame retarded rigid polyurethane foams plastics and preparation method thereof |
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| CN201910348766.1A CN110283351A (en) | 2019-04-28 | 2019-04-28 | A kind of flame retarded rigid polyurethane foams plastics and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113209539A (en) * | 2021-05-17 | 2021-08-06 | 重庆工程职业技术学院 | Coal mine composite colloid fire prevention and extinguishing material and preparation method thereof |
| CN113717515A (en) * | 2021-08-23 | 2021-11-30 | 安徽瑞琦塑胶科技有限公司 | Antistatic heat-insulating plastic pipe and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50119059A (en) * | 1974-02-20 | 1975-09-18 | ||
| DE3035466A1 (en) * | 1979-09-19 | 1981-04-09 | Tenneco Chemicals Inc., 07662 Saddle Brook, N.J. | POLYURETHANE SOFT FOAMS AND METHOD FOR THE PRODUCTION THEREOF |
| CN102675860A (en) * | 2012-05-11 | 2012-09-19 | 上海化工研究院 | Halogen-free flame-retardant polyurethane hard bubble heat preserving material and preparation method thereof |
| CN103030780A (en) * | 2012-12-31 | 2013-04-10 | 南京弘诺科技有限公司 | Flame-retardant polyurethane modified polyisocyanurate foam, and preparation method and application of foam |
-
2019
- 2019-04-28 CN CN201910348766.1A patent/CN110283351A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50119059A (en) * | 1974-02-20 | 1975-09-18 | ||
| DE3035466A1 (en) * | 1979-09-19 | 1981-04-09 | Tenneco Chemicals Inc., 07662 Saddle Brook, N.J. | POLYURETHANE SOFT FOAMS AND METHOD FOR THE PRODUCTION THEREOF |
| CN102675860A (en) * | 2012-05-11 | 2012-09-19 | 上海化工研究院 | Halogen-free flame-retardant polyurethane hard bubble heat preserving material and preparation method thereof |
| CN103030780A (en) * | 2012-12-31 | 2013-04-10 | 南京弘诺科技有限公司 | Flame-retardant polyurethane modified polyisocyanurate foam, and preparation method and application of foam |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113209539A (en) * | 2021-05-17 | 2021-08-06 | 重庆工程职业技术学院 | Coal mine composite colloid fire prevention and extinguishing material and preparation method thereof |
| CN113717515A (en) * | 2021-08-23 | 2021-11-30 | 安徽瑞琦塑胶科技有限公司 | Antistatic heat-insulating plastic pipe and preparation method thereof |
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