CN106633011A - Reaction type flame-retardant polyester polyol and preparation method thereof - Google Patents
Reaction type flame-retardant polyester polyol and preparation method thereof Download PDFInfo
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- CN106633011A CN106633011A CN201611256645.7A CN201611256645A CN106633011A CN 106633011 A CN106633011 A CN 106633011A CN 201611256645 A CN201611256645 A CN 201611256645A CN 106633011 A CN106633011 A CN 106633011A
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- Prior art keywords
- reaction
- type flame
- retarding
- pepa
- flame
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4607—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen having halogens
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- 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
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- 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
Abstract
The invention relates to a method for preparing a reaction type flame-retardant polyester polyol. The reaction type flame-retardant polyester polyol comprises the following raw materials in parts by mass: 45-50 parts of tetrachlorophthalic anhydride, 40-45 parts of polyhydric alcohols, 5-10 parts of a phosphorus-containing flame retardant, 0.003-0.005 part of an antioxidant and 0.005-0.01 part of a catalyst. The method for preparing the reaction type flame-retardant polyester polyol disclosed by the invention overcomes the defects of additive flame-retardant polyesters, has the characteristics of environment friendliness, high efficiency, low toxicity and long-lasting effect, and plays a more and more important role in flame retardancy study of the polyurethane. The polyester polyol prepared by the method has a phosphorus-halogen compound flame-retardant effect, so the polyester polyol has excellent and long-lasting flame-retardant property. Moreover, due to high degree of functionality, the prepared hard bubble has excellent strength and can be widely applied to hard bubbles of spray and piping.
Description
Technical field
The invention belongs to the preparation method field of chemical products, and in particular to a kind of system of reaction-type flame-retarding PEPA
Preparation Method.
Background technology
Polyurethane is the high polymer containing carbamate groups (- NHCOO-) in molecule chain.With former during synthesis
The difference of material, auxiliary agent and process conditions, can with the different product of synthesis performance, such as foamed plastics, rubber, coating, adhesive,
Elastomer etc..Polyurethane foam is the current optimal heat-insulating material of performance in the world, due to the developed countries such as America and Europe height
DEG C pay attention to building energy conservation, so in these countries, hard polyurethane foam have been widely used for the roof of building, body of wall, ceiling,
Floor, door and window etc..But, close DEG C of polyurethane foam plastics is little, and specific surface area is big, easily fires compared with non-foam material
Burn, burning and decomposition produce substantial amounts of toxic smog.Meeting fire can burn and decompose, and Heat liberation unit is big during burning, and generation has in a large number
Toxic smoke mist, has very bad impact to health and environment.Therefore, the flame resistance of RPUF, security,
Can become be used for the important technology index of insulation material.National governments also promulgate a decree and regulation in succession, clear stipulaties
Under a little occasions, the use of polyurethane material must reach certain flame-retardant standard, and the appearance of various regulations advances resistance significantly
The development of combustion technology.
PEPA is a purposes class chemical intermediate widely, and it is mainly for the production of polyurethane product, bag
Include thermoplastic polyurethane, soft polyurethane foam, hard polyurethane foam, solvent type polyurethane resin and waterborne polyurethane resin etc..
Compared with additive flame retardant, reactive flame retardant has that addition is few, little to the Effect on Mechanical Properties of material, resistance
Combustion persistence it is good the advantages of and be widely used.Phosphorus it is fire-retardant with environmental protection, efficiently, low toxicity the characteristics of, in polyurethane flame-proof research
Middle to play more and more important effect, because halogen and P elements have synergy, therefore the present invention has synthesized a kind of new
Phosphorous halogen flame retardant polyester polyalcohol.
The content of the invention
It is an object of the invention to provide a kind of preparation method of reaction-type flame-retarding PEPA, overcomes additive flame retardant to gather
The deficiency of ester, with environmental protection, efficiently, low toxicity, it is permanent the characteristics of, play more and more important work in polyurethane flame-proof research
With.Ignition-proof element phosphorus or halogen are imported at the same time or separately in polyalcohol by chemical reaction, with fire resistance reaction-type flame-retarding
Agent participates in reacting as a kind of reacted constituent, little to Effect of Materials performance, and it is stable to be attached in polyurethane matrix, makes poly- ammonia
Ester contains in itself flame-retardant composition, will not separate out in Long-Time Service process and reduce fire resistance.The polyester prepared with the method is more
First alcohol has phosphorus halogen compositional flame-retardant effect, therefore with fire resistance that is excellent and can keeping for a long time, and due to higher sense
What degree made to be made hard bubbles extraordinary intensity, can be widely used in spraying and pipeline-like hard bubbles.
Described reaction-type flame-retarding PEPA, in terms of mass fraction, raw material composition is as follows：
Tetrachlorophthalic anhydride is 45-50 parts, and polyalcohol is 40-45 parts, and phosphonium flame retardant is 5-10 parts, and antioxidant is 0.003-
0.005 part, catalyst is 0.005-0.01 parts.
The polyalcohol is one or two in dihydroxylic alcohols, trihydroxylic alcohol.
Dihydroxylic alcohols is the one kind in ethylene glycol, diethylene glycol (DEG), neopentyl glycol or butanediol, and trihydroxylic alcohol is glycerine or trihydroxy methyl
One kind in propane.
Described antioxidant is 1010, and described catalyst is the one kind in tetrabutyl titanate or organotin catalysts,
Preferably tetrabutyl titanate, described phosphonium flame retardant is phosphate, phosphite ester, organophosphorated salt, phosphorous heterocylic compound or poly-
Compound phosphate.
Described phosphonium flame retardant adds quality in 5-10%.
The preparation method of described reaction-type flame-retarding PEPA, with tetrachlorophthalic anhydride as initiator, with polyol copolymer
Reaction, and antioxidant and catalyst are added, the PEPA of hydroxyl value 200-300mgKOH/g is obtained, add phosphor-containing flame-proof
Agent is obtained reaction-type flame-retarding PEPA.
The degree of functionality of reaction-type flame-retarding PEPA is between 2-3.
Obtained reaction-type flame-retarding PEPA is used for hard polyurethane foam.
The preparation method of reaction-type flame-retarding PEPA, step is as follows：
Using progressively temperature-raising method, when temperature is raised to 135-145 DEG C of beginning water outlet, temperature 95-110 of reflux column is controlled
DEG C, then kettle temperature is slowly raised to into 155-165 DEG C, constant temperature 2-3 hours, afterwards in the way of progressively heating up, in 6-7 hours by temperature
Degree is raised to 220-230 DEG C, when water outlet is finished, is incubated 0.8-1.2 hours, and beginning is progressively vacuumized, when hydroxyl value reaches 200-
During 300mgKOH/g, stop vacuumizing and cooling to 80 DEG C, obtain the PEPA.
By the hydroxyl value of reaction-type flame-retarding PEPA obtained in the present invention in 200-300mg KOH/g.
It is of the present invention to prepare in PEPA, polyalcohol used be preferably ethylene glycol, diethylene glycol, new penta 2
Two kinds in alcohol or butanediol, trimethylolpropane, glycerine, one of which is dihydroxylic alcohols, a kind of for trihydroxylic alcohol, preferred proportion
Mass fraction for dihydroxylic alcohols is 30-35 parts, trimethylolpropane or glycerine 10-15 parts.
Compared with prior art, the invention has the advantages that：
The preparation method of reaction-type flame-retarding PEPA of the present invention, overcomes the shortcomings of additive flame retardant polyester, with ring
Protect, efficiently, low toxicity, it is permanent the characteristics of, play more and more important effect in polyurethane flame-proof research.By ignition-proof element phosphorus
Or halogen is imported at the same time or separately in polyalcohol by chemical reaction, is reacted into as one kind with fire resistance reactive flame retardant
Point participate in reaction, little to Effect of Materials performance, it is stable to be attached in polyurethane matrix, make polyurethane itself contain it is fire-retardant into
Point, will not separate out in Long-Time Service process and reduce fire resistance.There is the PEPA prepared with the method phosphorus halogen to compound
Fire retarding effect, therefore with fire resistance that is excellent and can keeping for a long time, and because higher degree of functionality hard bubbling of making to be made has
Extraordinary intensity, can be widely used in spraying and pipeline-like hard bubbles.
Specific embodiment
The present invention is done into a line with reference to embodiment and illustrated, but be not limitation of the present invention.
Embodiment 1
By weight by 45 parts of tetrachlorophthalic anhydride, 30 parts of diethylene glycol, 15 parts of glycerine, 0.003 part of antioxidant 1010, titanium
0.005 part of sour N-butyl, is added in reactor and heats, and logical nitrogen protection, when temperature is raised to 145 DEG C of beginning water outlets, control
The temperature of reflux column is 95 DEG C, then kettle temperature is slowly raised to into 155 DEG C, constant temperature 2 hours, afterwards in the way of progressively heating up, 6
Temperature is raised to 230 DEG C by hour, when water outlet is finished, is incubated 1 hour, and beginning is progressively vacuumized, and after 3 hours sampling detecting acid number is started
And hydroxyl value, as acid number ＜ 2.0 (mgKOH/g), when hydroxyl value is to 200mgKOH/g, stop vacuumizing, start cooling, when temperature reaches
Add 5 parts of phosphite esters, stirring to resample measure after 30 minutes when 100 DEG C, after indices are up to standard blowing is started, obtain final product
Flame retardant polyester polyalcohol.
Embodiment 2
By weight by 50 parts of tetrachlorophthalic anhydride, 34 parts of butanediol, 10 parts of trimethylolpropane, antioxidant 1010 0.004
Part, 0.006 part of tetrabutyl titanate is added in reactor and heats, and logical nitrogen protection, when temperature is raised to 135 DEG C of beginning water outlets,
The temperature for controlling reflux column is 101 DEG C, then kettle temperature is slowly raised to into 160 DEG C, constant temperature 3 hours, afterwards the side progressively to heat up
Formula, 230 DEG C were raised at 6.5 hours by temperature, when water outlet is finished, were incubated 1 hour, and beginning is progressively vacuumized, and starts to take after 3 hours
Sample surveys acid number and hydroxyl value, as acid number ＜ 2.0 (mgKOH/g), hydroxyl value to 200 (mgKOH/g), stops vacuumizing, and starts cooling,
6 parts of triphosphoric acid ethyl esters, stirring are added to resample measure after 30 minutes when temperature reaches 100 DEG C, after indices are up to standard
Start blowing, obtain final product flame retardant polyester polyalcohol.
Embodiment 3
By weight by 48 parts of tetrachlorophthalic anhydride, 33 parts of neopentyl glycol, 11 parts of glycerine, 0.005 part of antioxidant 1010, titanium
0.007 part of sour N-butyl, is added in reactor and heats, and logical nitrogen protection, when temperature is raised to 140 DEG C of beginning water outlets, control
The temperature of reflux column is 105 DEG C, then kettle temperature is slowly raised to into 165 DEG C, constant temperature 2 hours, afterwards in the way of progressively heating up,
Temperature was raised to into 220 DEG C in 7 hours, when water outlet is finished, is incubated 1.2 hours, beginning is progressively vacuumized, sampling is started after 3 hours and is surveyed
Acid number and hydroxyl value, as acid number ＜ 2.0 (mgKOH/g), hydroxyl value to 200 (mgKOH/g), stop vacuumizing, and start cooling, work as temperature
Add 8 parts of triphosphoric acid ethyl esters when degree reaches 100 DEG C, stirring is resampled measure after 30 minutes, start after indices are up to standard
Blowing, obtains final product flame retardant polyester polyalcohol.
Embodiment 4
By weight by 45 parts of tetrachlorophthalic anhydride, 35 parts of ethylene glycol, 10 parts of trimethylolpropane, antioxidant 1010 0.003
Part, 0.008 part of tetrabutyl titanate is added in reactor and heats, and logical nitrogen protection, when temperature is raised to 140 DEG C of beginning water outlets,
The temperature for controlling reflux column is 110 DEG C, then kettle temperature is slowly raised to into 155 DEG C, constant temperature 3 hours, afterwards the side progressively to heat up
Formula, 225 DEG C were raised at 7 hours by temperature, when water outlet is finished, were incubated 0.8 hour, and beginning is progressively vacuumized, and starts to take after 3 hours
Sample surveys acid number and hydroxyl value, as acid number ＜ 2.0 (mgKOH/g), hydroxyl value to 200 (mgKOH/g), stops vacuumizing, and starts cooling,
9 parts of triphosphoric acid ethyl esters, stirring are added to resample measure after 30 minutes when temperature reaches 100 DEG C, after indices are up to standard
Start blowing, obtain final product flame retardant polyester polyalcohol.
Claims (9)
1. a kind of reaction-type flame-retarding PEPA, it is characterised in that in terms of mass fraction, raw material composition is as follows：Tetrachlorophthalic anhydride
For 45-50 parts, polyalcohol is 40-45 parts, and phosphonium flame retardant is 5-10 parts, and antioxidant is 0.003-0.005 parts, and catalyst is
0.005-0.01 parts.
2. reaction-type flame-retarding PEPA according to claim 1, it is characterised in that the polyalcohol be dihydroxylic alcohols,
One or two in trihydroxylic alcohol.
3. reaction-type flame-retarding PEPA according to claim 2, it is characterised in that dihydroxylic alcohols is ethylene glycol, two sweet
One kind in alcohol, neopentyl glycol or butanediol, trihydroxylic alcohol is glycerine or the one kind in trimethylolpropane.
4. reaction-type flame-retarding PEPA according to claim 1, it is characterised in that described antioxidant is
1010, described catalyst is tetrabutyl titanate or the one kind in organotin catalysts, described phosphonium flame retardant be phosphate,
Phosphite ester, organophosphorated salt, phosphorous heterocylic compound or polymeric phosphoric acid ester.
5. reaction-type flame-retarding PEPA according to claim 1, it is characterised in that described phosphonium flame retardant addition
Quality is in 5-10%.
6. the preparation method of the reaction-type flame-retarding PEPA described in a kind of claim 1, it is characterised in that with tetrachlorophthalic anhydride
For initiator, react with polyol copolymer, and add antioxidant and catalyst, obtain the polyester of hydroxyl value 200-300mgKOH/g
Polyalcohol, adds phosphonium flame retardant and reaction-type flame-retarding PEPA is obtained.
7. the preparation method of reaction-type flame-retarding PEPA according to claim 6, it is characterised in that reaction-type flame-retarding
The degree of functionality of PEPA is between 2-3.
8. the preparation method of reaction-type flame-retarding PEPA according to claim 6, it is characterised in that obtained reaction
Type flame retardant polyester polyalcohol is used for hard polyurethane foam.
9. the preparation method of reaction-type flame-retarding PEPA according to claim 6, it is characterised in that step is as follows：
Using progressively temperature-raising method, when temperature is raised to 135-145 DEG C of beginning water outlet, temperature 95-110 DEG C of reflux column is controlled, so
Afterwards kettle temperature is slowly raised to into 155-165 DEG C, constant temperature 2-3 hours, afterwards in the way of progressively heating up, in 6-7 hours by temperature liter
To 220-230 DEG C, when water outlet is finished, 0.8-1.2 hours are incubated, beginning is progressively vacuumized, when hydroxyl value reaches 200-300mgKOH/
During g, stop vacuumizing and cooling to 80 DEG C, obtain the PEPA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611256645.7A CN106633011A (en) | 2016-12-30 | 2016-12-30 | Reaction type flame-retardant polyester polyol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611256645.7A CN106633011A (en) | 2016-12-30 | 2016-12-30 | Reaction type flame-retardant polyester polyol and preparation method thereof |
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| CN106633011A true CN106633011A (en) | 2017-05-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201611256645.7A Pending CN106633011A (en) | 2016-12-30 | 2016-12-30 | Reaction type flame-retardant polyester polyol and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003420A (en) * | 2019-04-17 | 2019-07-12 | 南京和润隆环保科技有限公司 | A kind of poly-isocyanurate foaming material and preparation method thereof |
| CN110229322A (en) * | 2019-05-20 | 2019-09-13 | 上海东睿化学有限公司 | Flame retardant polyester polyalcohol and preparation method and applications |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044673A (en) * | 2012-12-29 | 2013-04-17 | 四川东材科技集团股份有限公司 | Preparation method of reaction type halogen-free phosphorous flame retardant polyester polyol |
| CN104130368A (en) * | 2014-07-21 | 2014-11-05 | 万华节能科技集团股份有限公司 | Flame-retardant polyurethane cast rigid foamed plastic sheet |
-
2016
- 2016-12-30 CN CN201611256645.7A patent/CN106633011A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044673A (en) * | 2012-12-29 | 2013-04-17 | 四川东材科技集团股份有限公司 | Preparation method of reaction type halogen-free phosphorous flame retardant polyester polyol |
| CN104130368A (en) * | 2014-07-21 | 2014-11-05 | 万华节能科技集团股份有限公司 | Flame-retardant polyurethane cast rigid foamed plastic sheet |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003420A (en) * | 2019-04-17 | 2019-07-12 | 南京和润隆环保科技有限公司 | A kind of poly-isocyanurate foaming material and preparation method thereof |
| CN110229322A (en) * | 2019-05-20 | 2019-09-13 | 上海东睿化学有限公司 | Flame retardant polyester polyalcohol and preparation method and applications |
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Application publication date: 20170510 |