CN104844777A - Preparation method of soybean oil-based flame-retardant hard polyurethane foam - Google Patents

Preparation method of soybean oil-based flame-retardant hard polyurethane foam Download PDF

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Publication number
CN104844777A
CN104844777A CN201510195699.6A CN201510195699A CN104844777A CN 104844777 A CN104844777 A CN 104844777A CN 201510195699 A CN201510195699 A CN 201510195699A CN 104844777 A CN104844777 A CN 104844777A
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China
Prior art keywords
soybean oil
preparation
rigid foam
polyurethane flame
oil based
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Pending
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CN201510195699.6A
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Chinese (zh)
Inventor
王念贵
王小婷
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Hubei University
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Hubei University
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Priority to CN201510195699.6A priority Critical patent/CN104844777A/en
Publication of CN104844777A publication Critical patent/CN104844777A/en
Pending legal-status Critical Current

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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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • C08G18/14—Manufacture of cellular products
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • 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
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Abstract

The invention relates to a preparation method of soybean oil-based flame-retardant hard polyurethane foam. The polyurethane foam is composed of a component A and a component B. The component A comprises polyol, a foaming agent and a catalyst, and the component B is isocyanate. The preparation method comprises the following steps: reacting soybean oil-based polyol with tri(hydroxymethyl) phosphine oxide and the catalyst according to a certain ratio to obtain the polyol, adding water as the foaming agent, uniformly stirring, adding the component B toluene diisocyanate, and uniformly stirring; and putting the above obtained mixture in an oven, and foaming for a period of time in order to obtain the soybean oil-based flame-retardant hard polyurethane foam.

Description

A kind of preparation method of soybean oil based polyurethane flame-proof rigid foam
Technical field
The present invention relates to a kind of preparation method of soybean oil based polyurethane flame-proof rigid foam, be specifically related to a kind of polyurethane flame-proof rigid foam with flame retardant effect.
Background technology
Along with the raising of social development and people's living standard, the demand of petroleum chemicals is day by day increased.Therefore the series of problems such as environmental pollution and petroleum products shortage is caused.Also the research of bio-based materials is made more and more to come into one's own.Soybean oil is a kind of undersaturated triglyceride level, and its fatty acid component mainly comprises stearic acid, oleic acid, linoleic acid plus linolenic acid.Soybean oil, except renewable, also has the advantages such as cheap and biodegradable, is the alternate resources of producing macromolecular material.By introducing the epoxy soybean oil that epoxy-modified soybean oil obtains functionalization on the unsaturated fatty acids of soybean oil.Then with methyl alcohol, open loop is carried out to epoxy soybean oil and can obtain soybean oil based polyvalent alcohol.
Hard polyurethane foam is a kind of macromolecular material of superior performance, because this thermal insulation of materials is effective, physical strength is high, soundproof effect is excellent and be widely used in every field.But because polyurethane foam density is little, specific surface area is greatly very easily lighted and burns.Therefore, to the research of polyurethane foam flame-retarded technology, there is very real meaning.
Soybean oil base polyol and the polyvalent alcohol prepared by the mixing of trishydroxymethyl phosphine oxide and the soybean oil based hard polyurethane foam prepared by vulcabond is utilized to have fire-retardant and environmental protection two-fold advantage.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of soybean oil based polyurethane flame-proof rigid foam.
The preparation of described soybean oil based polyurethane flame-proof rigid foam of the present invention, concrete operation step is as follows:
Step a, by soybean oil base polyol, trishydroxymethyl phosphine oxide and 1 ~ 3% catalyzer add in beaker, stir fast, at 30 ~ 100 DEG C react 4 ~ 6min;
Step b, tolylene diisocyanate is added in beaker, stir fast, at 30 ~ 100 DEG C, react 4 ~ 5min.Obtain intermediate product.Then add water as whipping agent, stir fast, react 4 ~ 5min at 30 ~ 100 DEG C after, put into baking oven, polyurethane flame-proof rigid foam can be obtained at 30 ~ 100 DEG C of foaming 10 ~ 100min.
Trishydroxymethyl phosphine oxide in step a and the mass ratio of soybean oil base polyol are 1:2 ~ 8.
Catalyzer in step a is diethanolamine or trolamine or thanomin.
Tolylene diisocyanate in step b is Toluene-2,4-diisocyanate, 6-vulcabond or Toluene-2,4-diisocyanate, 4-vulcabond.
In step b, tolylene diisocyanate and the amount of substance of the polyvalent alcohol described in a are than being 1:2 ~ 2.5.
Whipping agent in step b and the mass ratio of the polyvalent alcohol described in a are 1:100.
Advantage of the present invention and innovative point are: 1. utilize soybean oil base polyol as synthesis material, are conducive to environment protection and economic Sustainable development.2. using trishydroxymethyl phosphine oxide as synthesis material and fire retardant, there is efficient, smokeless, nontoxic advantage.
Embodiment
Below by specific embodiment, the invention will be further described:
Carry out the preparation of soybean oil based polyurethane flame-proof rigid foam in accordance with the following steps:
Step a, by soybean oil base polyol, trishydroxymethyl phosphine oxide and 1 ~ 3% catalyzer add in beaker, stir fast, at 30 ~ 100 DEG C react 4 ~ 6min;
Step b, tolylene diisocyanate is added in beaker, stir fast, at 30 ~ 100 DEG C, react 4 ~ 5min.Obtain intermediate product, then add water as whipping agent, stir fast, react 4 ~ 5min at 30 ~ 100 DEG C after, put into baking oven, polyurethane flame-proof rigid foam can be obtained at 30 ~ 100 DEG C of foaming 10 ~ 100min.
Specific embodiment is as follows:
Embodiment 1
Step a, be the soybean oil base polyol of 4.00g by quality, quality is the trishydroxymethyl phosphine oxide of 1.00g, 3 diethanolamine add in beaker, stir fast, at 50 DEG C, react 6min;
Step b, the Toluene-2,4-diisocyanate being 2:1 by the amount ratio with polyol agent, 6-vulcabond adds in beaker, stirs fast, at 50 DEG C, react 5min.Then add 2 instillation water as whipping agent, stir fast, at 50 DEG C, react 5min.Finally put into baking oven, polyurethane flame-proof rigid foam can be obtained at 50 DEG C of foaming 60min.
Embodiment 2
Step a, be the soybean oil base polyol of 4.00g by quality, quality is the trishydroxymethyl phosphine oxide of 1.00g, 3 diethanolamine add in beaker, stir fast, at 60 DEG C, react 6min;
Step b, the Toluene-2,4-diisocyanate being 2:1 by the amount ratio with polyol agent, 4-vulcabond adds in beaker, stirs fast, at 60 DEG C, react 5min.Then adding 3 drips as whipping agent, stirs fast, at 60 DEG C, react 5min.Finally put into baking oven, polyurethane flame-proof rigid foam can be obtained at 60 DEG C of foaming 60min.
Embodiment 3
Step a, be the soybean oil base polyol of 4.50g by quality, quality is the trishydroxymethyl phosphine oxide of 1.00g, 3 diethanolamine add in beaker, stir fast, at 50 DEG C, react 6min;
Step b, the Toluene-2,4-diisocyanate being 2:1 by the amount ratio with polyol agent, 6-vulcabond adds in beaker, stirs fast, at 50 DEG C, react 5min.Then adding 2 drips as whipping agent, stirs fast, at 50 DEG C, react 5min.Finally put into baking oven, polyurethane flame-proof rigid foam can be obtained at 50 DEG C of foaming 60min.
The soybean oil based polyurethane flame-proof rigid foam prepared by above-mentioned different embodiment is all had the following advantages: 1. utilize soybean oil base polyol as synthesis material, is conducive to environment protection and economic Sustainable development.2. using trishydroxymethyl phosphine oxide as synthesis material and fire retardant, there is efficient, smokeless, nontoxic advantage.

Claims (6)

1. a preparation method for soybean oil based polyurethane flame-proof rigid foam, is characterized in that comprising the following steps:
Step a, by soybean oil base polyol, trishydroxymethyl phosphine oxide and 1 ~ 3% catalyzer add in beaker, stir fast, at 30 ~ 100 DEG C react 4 ~ 6min;
Step b, tolylene diisocyanate is added in beaker, stir fast, 4 ~ 5min is reacted at 30 ~ 100 DEG C, obtain intermediate product, then water is added as whipping agent, stir fast, react 4 ~ 5min at 30 ~ 100 DEG C after, put into baking oven, polyurethane flame-proof rigid foam can be obtained at 30 ~ 100 DEG C of foaming 10 ~ 100min.
2. the preparation method of a kind of soybean oil based polyurethane flame-proof rigid foam according to claim 1, is characterized in that: the trishydroxymethyl phosphine oxide in step a and the mass ratio of soybean oil base polyol are 1:2 ~ 8.
3. the preparation method of a kind of soybean oil based polyurethane flame-proof rigid foam according to claim 1, is characterized in that: the catalyzer in step a is diethanolamine or trolamine or thanomin.
4. the preparation method of a kind of soybean oil based polyurethane flame-proof rigid foam according to claim 1, is characterized in that: the tolylene diisocyanate in step b is Toluene-2,4-diisocyanate, 6-vulcabond or Toluene-2,4-diisocyanate, 4-vulcabond.
5. the preparation method of a kind of soybean oil based polyurethane flame-proof rigid foam according to claim 1, is characterized in that: in step b, tolylene diisocyanate and the amount of substance of the polyvalent alcohol described in a are than being 1:2 ~ 2.5.
6. the preparation method of a kind of soybean oil based polyurethane flame-proof rigid foam according to claim 1, is characterized in that: the whipping agent in step b and the mass ratio of the polyvalent alcohol described in a are 1:100.
CN201510195699.6A 2015-04-22 2015-04-22 Preparation method of soybean oil-based flame-retardant hard polyurethane foam Pending CN104844777A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105860020A (en) * 2016-04-19 2016-08-17 滁州环球聚氨酯科技有限公司 High-strength hydrophobic flame-retardant polyurethane cable outer sheath
CN106700022A (en) * 2017-01-18 2017-05-24 中国科学院长春应用化学研究所 Cationic waterborne polyurethane, preparation method thereof, coating composition and preparation method thereof
CN107840938A (en) * 2017-11-27 2018-03-27 山东诺威新材料有限公司 Combined polyether, ageing-resistant complete water type foam board and preparation method thereof
CN112175164A (en) * 2020-10-14 2021-01-05 浙江理工大学桐乡研究院有限公司 Preparation method of flame-retardant polyurethane foam

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105860020A (en) * 2016-04-19 2016-08-17 滁州环球聚氨酯科技有限公司 High-strength hydrophobic flame-retardant polyurethane cable outer sheath
CN106700022A (en) * 2017-01-18 2017-05-24 中国科学院长春应用化学研究所 Cationic waterborne polyurethane, preparation method thereof, coating composition and preparation method thereof
CN107840938A (en) * 2017-11-27 2018-03-27 山东诺威新材料有限公司 Combined polyether, ageing-resistant complete water type foam board and preparation method thereof
CN112175164A (en) * 2020-10-14 2021-01-05 浙江理工大学桐乡研究院有限公司 Preparation method of flame-retardant polyurethane foam

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Application publication date: 20150819

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