CN101792465B - Modifier of polyol ester phosphate and polyisocyanate, preparation method and application thereof - Google Patents
Modifier of polyol ester phosphate and polyisocyanate, preparation method and application thereof Download PDFInfo
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- CN101792465B CN101792465B CN200910216685A CN200910216685A CN101792465B CN 101792465 B CN101792465 B CN 101792465B CN 200910216685 A CN200910216685 A CN 200910216685A CN 200910216685 A CN200910216685 A CN 200910216685A CN 101792465 B CN101792465 B CN 101792465B
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Abstract
The invention discloses a method for preparing a modifier of polyol ester phosphate and polyisocyanate and application thereof. The method is characterized by comprising the following steps: adding raw materials in a molar ratio of alcohol to acid of 1:1.1-1.5, wherein the using amount of a water-carrying agent is one fourth of the weight of the raw materials; adding the mixture into a reactor with a mixer, a thermometer and a water knockout trap to perform reaction for 3 to 6 hours at the temperature of between 100 and 160 DEG C to obtain polyol ester; adding polyisocyanate accounting for 5 to 20 percent of the weight of the ester into the reactor with the mixer and the thermometer to perform reaction for 2 to 4 hours at the temperature of between 80 and 120 DEG C to obtain the modifier of the polyol ester and the polyisocyanate. The water solubility of the modifier of the polyol ester phosphate and the polyisocyanate is greatly reduced until the modifier disappears. The modified substance can be combined with phosphoric melamine salt, ammonium polyphosphate and other substances to prepare an intumescent flame retardant. When the intumescent flame retardant is used for flame retardancy of polyethylene, polypropylene and other polyolefin polymers with added amount in a range of between 30 and 35 percent (weight part), the flame retardant effect can reach V-0 grade through the UL-94 test.
Description
Technical field:
The present invention relates to polyol ester phosphate and modified polyisocyanate thing, belong to macromolecular material flame-retarded technology field.
Background technology
The polyolefins macromolecular material, its raw material is sufficient, and is synthetic and processing technology is ripe, excellent material performance, thus obtain application more and more widely in various fields such as wrapping material, mechanical engineering, electric, shipping vehicle, communication and power cables.Yet polyolefin plastics is again to be easy to the incendiary material, in numerous practical applications, mostly relates to the fire-retardant requirement to material.Therefore, when using as engineering plastics, polyolefine must pass through fire-retardant finish.
The flame-retarded technology scheme of macromolecular material roughly has two aspects, and the fire-retardant and halogen-free flameproof of halogen is arranged.Having halogen fire-retardant is a development of experiencing the long period, and the application of related prods is the flame-retarded technology of comparative maturity all, and relevant document is also very many.Its principal character through in macromolecular material, adding the halogen-containing organic cpds of some amount (also adding other synergy materials sometimes simultaneously), makes material have flame retardant resistance exactly.Polyolefine material such as Vilaterm, Vestolen PP 7052 can add halogen containing organic compound matter such as decabromodiphenyl oxide, clorafin, chlorinatedpolyethylene, and perhaps add part again and play synergistic inorganic combustion inhibitor, like Antimony Trioxide: 99.5Min, zinc borate etc.Although halogen-containing fire retardant is respond well comprising the technology maturation of polyolefinic numerous macromolecular material in fire-retardant, be based on following reason, there is the halogen flame-retarded technology to face that intensive is queried and blame in recent years.
1) added halogen-containing flame retardant in the macromolecular material, when fire took place, material can discharge a large amount of smog, in comprise poisonous and hazardous hydrogen halide, to the fire-fighting field staff sue and labour and work such as withdraw causes difficulty.
2) macromolecular material of halogen-containing based flame retardant can produce dioxin in follow-up recycling process, and environment is polluted.Dioxin has been proved to be the intensive carcinogenic substance.
Therefore, making great efforts not halogen-containing fire retardant of development and correlation technique, is people in the industry's responsibility, also is the only way of fire-retardant science.
Non-halogen Flame Retardant Technology is having the fire-retardant newly-developed afterwards of halogen, and this type technology adopts not halogen-containing fire retardant, and addition is general more than halogen fire retardant is arranged.Through the macromolecular material that halogen-free flameproof is handled, can not cause the problem of the fire-retardant that kind of halogen.Different macromolecular materials, its fire-retardant scheme is different certainly.Specific to the halogen-free flameproof of polyolefine materials such as Vilaterm, Vestolen PP 7052, mainly contain aluminium, magnesium oxyhydroxide scheme and expansion type flame-retarding scheme two big technical systems at present.Wherein, aluminium, magnesium oxyhydroxide scheme are to adopt white lake, Marinco H class powder material, add in the polyolefine later on through dispersion agent or coupling agent surface treatment.Like this, reach fire-retardant purpose in effects such as the dehydration through white lake or Marinco H of when burning, moisture vaporization coolings.Concrete grammar such as Chinese patent CN03153510.0, Mexico patent MX2008014081, bibliographical informations such as world patent WO2009105636; The expansion type flame-retarding scheme then is through phosphoric acid salt; SULPHOSUCCINIC ACID ESTER; The combination of material such as phosphoramide and polyhydroxy substance and some nitrogenous compound, perhaps the phosphorylated polyhydroxy substance again with some nitrogenous compound combination, make fire retardant systems contain so-called acid source, carbon source and source of the gas simultaneously; Like this when fire takes place fire retardant will be heat insulation through expand forming, the Carbon foam layer of oxygen barrier, difficult combustion, reach fire-retardant purpose.Like " chemical industry technological development, 2003,32 (6); Polymer material science and engineering, 2003,19 (6); The Tianjin chemical industry, 2006,20 (4) " etc. document is reported.
At present; Adopt white lake, Marinco H class inorganic mineral powder carries out fire-retardant to polyolefine, has that addition is excessive (generally will to be added more than 60% by weight; Enough flame retardant effects are just arranged) shortcoming; And this based flame retardant itself differs far away with polyolefinic surface properties, in case addition is excessive, it is bad that the physical and mechanical properties of material obviously becomes.In order to solve the problem of this respect, to adopt to cooperate and add dispersion agent, measures such as compatilizer and coupling agent can make material property make moderate progress to a certain extent, but still unresolved root problem.Meanwhile, adopt the expanded polystyrene veneer scheme technology fire-retardant, developed preferably polyolefine material.Wherein, especially with the expansion type flame-retarding system of composite formations such as the polyol ester phosphate compounds or derivatives thereof of various structures and ammonium polyphosphate, addition moderate (generally by weight about 25%-35%), flame retardant effect is good, thereby noticeable.At present, employed ammonium polyphosphate (APP) has been sophisticated industrialization product in many countries such as China in the above-mentioned expansion type flame-retarding system formulation.And related polyol ester phosphate class material in the prescription, because below, the situation of aspect industriallization, still slowly not opening:
1) broken away from not the puzzlement of problems such as raw material POCl3 and the discharging of product building-up process hydrogenchloride.
Present most investigator synthesizes polyol ester phosphate, all sets out with POCl3, and with tetramethylolmethane, polyol reactions such as NSC 6366 (esterification) are emitted hydrogenchloride simultaneously, like " Speciality Petrochemicals, 1993,6; Additives for plastics, 2007,4; GB2458058; US2009163627 " etc. document said.Its typical reaction is:
POCl3 is swift in response with hydroxyl groups as a kind of acyl chlorides, and esterification is complete.Obtain the SULPHOSUCCINIC ACID ESTER of a series of ring-types or cage structure thus, the importance of verified these polyol ester phosphates of lot of documents in numerous macromolecular material expandable flame retardant prescriptions.Yet the raw material POCl3 is again a kind of hazardous chemical, making, the danger of blast is arranged all in accumulating and the use; Moreover, with the POCl3 manufacturing polyol ester phosphate that sets out, must discharge not only strong corrosion equipment but also environmentally harmful hydrogen chloride gas in a large number, these factors all are that the industrialization of polyol ester phosphate brings no small obstacle.
2) cost is high, and product marketization is obstructed
Because its technological process of method that above-mentioned dependence POCl3 is a raw material is dangerous and complicated; And the release of corrosive salt acid gas needs the great number economy input of ME and environmental improvement aspects; Cause the production cost of these class methods always higher, cause the industrialization promotion of polyol ester phosphate class fire retardant matter for many years not smooth always.
In fact; Can the direct esterification reaction generate polyol ester phosphate class material through phosphoric acid under proper condition with relevant polyvalent alcohol, this class process does not have the phosphoryl chloride method such dangerous and complicated, does not produce environmentally hazardous emission gases yet; The material that is obtained has clear and definite effect equally in flame-retardant formulations; Of documents such as " chemical research and application, 2009,4 ".Yet; The direct esterification legal system is equipped with polyol ester phosphate, and esterification is complete not as chloride method, and reacting resulting is the incomplete carboxylate of remaining part of hydroxyl mostly; Though their flame retardant properties is also good; But hydroxyl remaining in the molecular structure belongs to hydrophilic radical, makes the water-soluble excessive of fire retardant, certainly will influence the range of application of material.If the hydroxy number in the product molecular structure that the direct esterification method is obtained further reduces; Its water tolerance is improved; Just might make direct esterification method this not only simple economy but also eco-friendly technology, become the feasible industrialized process for preparing of flame retardant resistance polyol ester phosphate.
Summary of the invention
The objective of the invention is to provide polyol ester phosphate and modified polyisocyanate thing, be characterized in reacting, make a series of polyol ester phosphate compounds through phosphoric acid and polyvalent alcohol direct esterification to the deficiency of prior art.Then, utilize remaining hydroxyl and POLYMETHYLENE POLYPHENYLISOCYANATE reaction in the polyol ester phosphate thing, obtain modifier.Though this speed of response through direct esterification legal system polyol ester phosphate is slower, raw materials cost is low, simple to operate, safety, and do not have the discharging of hydrogen chloride gas, environmentally friendly.The modification of POLYMETHYLENE POLYPHENYLISOCYANATE is also fairly simple, carries out easily.The modifier that the product that obtains with the direct esterification method is the basis is the same with the chloride method product to have good flame retardancy to the polyolefins polymer.
The object of the invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
Polyol ester phosphate and modified polyisocyanate thing and preparation method thereof
The chemical reaction formula of part is following in polyol ester phosphate and the preparation of modified polyisocyanate thing:
1) direct esterification of phosphoric acid and polyvalent alcohol:
2) reaction of esterification products and POLYMETHYLENE POLYPHENYLISOCYANATE:
The preparation method of polyol ester phosphate and modified polyisocyanate thing may further comprise the steps:
(1) with raw alcohol: acid=1: the 1.1-1.5 mol ratio feeds intake, and band aqua consumption is 1/4 of a raw material input weight, adds and has whisking appliance, in the reactor drum of TM and reflux exchanger, in temperature 100-160 ℃ of reaction 3-6 hour, obtains polyol ester;
(2) 5-20% of POLYMETHYLENE POLYPHENYLISOCYANATE by carboxylate weight fed intake, add and have whisking appliance, in the reactor drum of TM and reflux exchanger,, obtain the modifier of polyol ester and POLYMETHYLENE POLYPHENYLISOCYANATE in temperature 80-120 ℃ of reaction 2-4 hour.
Polyvalent alcohol is a terepthaloyl moietie, NSC 6366, USP Kosher, any in TriMethylolPropane(TMP) or the tetramethylolmethane.
POLYMETHYLENE POLYPHENYLISOCYANATE is 4,4 '-diphenylmethanediisocyanate, any in tolylene diisocyanate or the many penylenes POLYMETHYLENE POLYPHENYLISOCYANATE.
Catalyzer is a diethylenetriamine, triethylene tetramine, polyethylene polyamine, dibutyl tin laurate, any in the stannous octoate.
Prepare polyol ester phosphate and modified polyisocyanate thing as stated above.
Polyol ester phosphate and modified polyisocyanate thing are used for the fire-retardant of polyolefine material.
Performance test
The water-soluble of the modifier of polyol ester phosphate and POLYMETHYLENE POLYPHENYLISOCYANATE declined to a great extent, until disappearance.This modified material and phosphoric melamine salt (MP); Ammonium polyphosphate materials such as (APP) cooperates forms expansion type flame retardant, is used for Vilaterm, and polyolefine such as Vestolen PP 7052 are high molecular fire-retardant; Addition is in 30-35% (weight part) scope, and flame retardant effect reaches the V-0 level through the UL-94 test.
The present invention has following advantage:
1) phosphoric acid and polyvalent alcohol direct esterification reaction system polyol ester phosphate thing, raw material is easy to get, and technological operation is simple, and environmental friendliness; Isocyanic ester further reacts away the remaining hydroxyl of carboxylate to the modification of polyol ester phosphate, and its water tolerance is improved, thereby satisfies the needs of engineering materials;
2) compare with the phosphoryl chloride preparation polyol ester phosphate technology of setting out, the inventive method cost of manufacture is lower.The esterification products that above modified polyisocyanate is later; Make its particle reach predetermined fineness through equipment milled processed such as ball mill, more according to a certain percentage with phosphoric melamine salt (MP), ammonium polyphosphate (APP) material of etc.ing cooperates the composition expansion type flame retardant; Be used for Vilaterm; Polyolefine such as Vestolen PP 7052 are high molecular fire-retardant, and addition can reach good effect in 30-35% (weight part) scope.Such result compares with the flame retardant effect of chloride method synthetic polyol ester phosphate, and is more approaching.And method raw material of the present invention is cheap, and technology is simple, safety, and environmental friendliness, thereby better industrial prospect is arranged.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary that again this is pointed out that present embodiment only is used for further specifying what the present invention carried out; Can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1
(1) direct esterification method is synthesized polyol ester phosphate
With hexanaphthene 58.8g, NSC 6366 114.4g (1.1mol), adding has in the reactor drum of whisking appliance, TM and water trap; In 100 ℃ of temperature, keep this temperature, begin to drip phosphoric acid; The phosphoric acid total amount is 121g (1.0mol), and the dropping time is 1.5h, and the moisture content that reaction process generates is taken out of through the hexanaphthene azeotropic; Be warming up to 120 ℃, continue to keep this temperature 1.5h, to strengthen esterification.At last, steam all band aquas, obtain thick phosphoric acid DOPCP;
2) preparation of phosphoric acid DOPCP and modified polyisocyanate thing
With above-mentioned phosphoric acid DOPCP 100g, 4,4 '-diphenylmethanediisocyanate 10g; Diethylenetriamine 0.275g, adding has in the reactor drum of whisking appliance, TM, in 110 ℃ of temperature; Sustained reaction 2h; Acquisition phosphoric acid DOPCP and 4,4 '-the diphenylmethanediisocyanate modifier, modifier is blocks of solid.
Through above modifying process, the water-soluble obvious reduction of polyol ester phosphate, even disappear.See for details shown in the table 1, the result shows that the water-soluble consumption with properties-correcting agent of modifier increases and reduces.
Phosphoric acid DOPCP and 4,4 '-application of diphenylmethanediisocyanate modifier in the Vestolen PP 7052 expandable flame retardant
With phosphoric acid DOPCP and 4,4 '-the diphenylmethanediisocyanate modifier is through ball mill grinding, reaches particle diameter below 40 μ m, gained powder and phosphoric melamine salt (MP) is made into mixture by weight at 1: 1, as expansion type flame retardant; On twin screw extruder; This based flame retardant is carried out thorough mixing in 30% ratio and acrylic resin (PP); On injection moulding machine, be injection molded into the standard batten then, and carry out the test of material vertical combustion, see for details shown in the table 2 by the UL-94 standard; The result shows that the flame retardant effect of this fire retardant in acrylic resin is good.
Embodiment 2
(1) direct esterification method is synthesized polyol ester phosphate
With toluene 58.8g, TriMethylolPropane(TMP) 154.1g (1.15mol), adding has in the reactor drum of whisking appliance, TM and water trap; In 110 ℃ of temperature; Keep this temperature, begin to drip phosphoric acid, the phosphoric acid total amount is 121g (1.0mol); The dropping time is 1.5h, and the moisture content that reaction process generates is taken out of through methylbenzene azeotropic.Be warming up to 130 ℃, continued to keep this temperature 2 hours, to strengthen esterification.At last, steam all band aquas, obtain thick phosphoric acid trihydroxymethylpropanyl ester.
(2) preparation of phosphoric acid trihydroxymethylpropanyl ester and modified polyisocyanate thing
With above-mentioned phosphoric acid trihydroxymethylpropanyl ester 100g, tolylene diisocyanate 11g, triethylene tetramine 0.275g; Adding has in the reactor drum of whisking appliance, TM, in 110 ° of temperature, and C sustained reaction 2.5h; Obtain phosphoric acid trihydroxymethylpropanyl ester and modified polyisocyanate thing, be blocks of solid.
Through above modifying process, the water-soluble obvious reduction of polyol ester phosphate, even disappear, it is said to see table 3 for details, and the result shows that the water-soluble consumption with properties-correcting agent of modifier increases and reduces.
The application of the modifier of phosphoric acid trihydroxymethylpropanyl ester and tolylene diisocyanate in the Vestolen PP 7052 expandable flame retardant
Phosphoric acid trihydroxymethylpropanyl ester and tolylene diisocyanate modifier are passed through ball mill grinding, and particle diameter is made into mixture with gained powder and phosphoric melamine salt (MP), as expansion type flame retardant by weight at 1: 1 below 40 μ m; On twin screw extruder; This based flame retardant is carried out thorough mixing in 35% ratio and acrylic resin (PP); On injection moulding machine, be injection molded into the standard batten then, and carry out the test of material vertical combustion, see for details shown in the table 4 by the UL-94 standard; The result shows that the flame retardant effect of this fire retardant in acrylic resin is good.
Embodiment 3
(1) direct esterification method is synthesized polyol ester phosphate
With YLENE 71g, tetramethylolmethane 163.2g (1.2mol), adding has in the reactor drum of whisking appliance, TM and water trap, in 120 ℃ of temperature, keeps this temperature, drips phosphoric acid, and the phosphoric acid total amount is 121g (1.0mol), and the dropping time is 1.5h.The moisture content that reaction process generates is taken out of through the YLENE azeotropic.Be warming up to 140 ℃, continue to keep this temperature 2.5h, to strengthen esterification.Steam all band aquas at last, obtain thick phosphoric acid pentaerythritol ester.
(2) preparation of the modified polyisocyanate thing of phosphoric acid pentaerythritol ester
With above-mentioned phosphoric acid pentaerythritol ester 100g, many penylenes POLYMETHYLENE POLYPHENYLISOCYANATE (PAPI) 12g, dibutyl tin laurate 0.336g; Adding has in the reactor drum of whisking appliance, TM, in 90 ℃ of temperature, sustained reaction 3h; Obtain the modified polyisocyanate thing of phosphoric acid pentaerythritol ester, be blocks of solid.
Through above modifying process, the water-soluble obvious reduction of polyol ester phosphate, even disappear, it is said to see table 5 for details, and the result shows that the water-soluble consumption with properties-correcting agent of modifier increases and reduces.
The application of the modifier of phosphoric acid pentaerythritol ester and many penylenes POLYMETHYLENE POLYPHENYLISOCYANATE in the Vestolen PP 7052 expandable flame retardant
The modifier of phosphoric acid pentaerythritol ester and many penylenes POLYMETHYLENE POLYPHENYLISOCYANATE is passed through ball mill grinding, and particle diameter is made into mixture with gained powder and ammonium polyphosphate (APP), as expansion type flame retardant by weight at 1: 1.5 below 40 μ m; On twin screw extruder, this based flame retardant is carried out thorough mixing in 32% ratio and polyvinyl resin (PE), on injection moulding machine, be injection molded into the standard batten then, and carry out the material vertical combustion by the UL-94 standard and measure.See for details shown in the table 6, the result shows that the flame retardant effect of this fire retardant in polyvinyl resin is good.
Table 1 phosphoric acid DOPCP and 4,4 '-the dissolving situation of modifier in water of diphenylmethanediisocyanate
*
| Properties-correcting agent consumption (%) | 0 | 2 | 5 | 10 | 12 | 15 |
| Solubleness (g/100g water) | 32 | 28 | 12 | 5 | 2 | 0 |
*-1) the properties-correcting agent POLYMETHYLENE POLYPHENYLISOCYANATE be 4,4 '-diphenylmethanediisocyanate (MDI); 2) the properties-correcting agent consumption is the weight percent of raw material SULPHOSUCCINIC ACID ESTER; 3) solubleness is measured in 25 ℃ of water.
The fire-retardant situation of the made expansion type flame retardant of table 2 in Vestolen PP 7052
| Fire retardant consumption (%), weight | 0 | 15 | 20 | 25 | 28 | 30 |
| UL-94 measures | Stepless | Stepless | V-2 | V-2 | V-1 | V-0 |
Table 3 phosphoric acid trihydroxymethylpropanyl ester and the tolylene diisocyanate modifier dissolving situation in water
*
| Properties-correcting agent consumption (%) | 0 | 2 | 5 | 10 | 12 | 15 |
| Solubleness (g/100g water) | 32 | 28 | 11 | 5 | 1.8 | 0 |
*-1) the properties-correcting agent POLYMETHYLENE POLYPHENYLISOCYANATE is a tolylene diisocyanate; 2) the properties-correcting agent consumption is the weight percent of former SULPHOSUCCINIC ACID ESTER; 3) solubleness is measured in 25 ℃ of water.
The fire-retardant situation of the made expansion type flame retardant of table 4 in Vestolen PP 7052
| Fire retardant consumption (%), weight | 0 | 15 | 20 | 25 | 28 | 30 |
| UL-94 measures | Stepless | Stepless | V-2 | V-2 | V-1 | V-0 |
[0072]The dissolving situation of the modifier of table 5 phosphoric acid pentaerythritol ester and many penylenes POLYMETHYLENE POLYPHENYLISOCYANATE in water
*
| Properties-correcting agent consumption (%) | 0 | 2 | 5 | 10 | 12 | 15 |
| Solubleness (g/100g water) | 32 | 29 | 13.5 | 6 | 3.5 | 0 |
*-1) the properties-correcting agent POLYMETHYLENE POLYPHENYLISOCYANATE is many penylenes POLYMETHYLENE POLYPHENYLISOCYANATE (PAPI); 2) the properties-correcting agent consumption is the weight percent of former SULPHOSUCCINIC ACID ESTER; 3) solubleness is measured in 25 ℃ of water.
The fire-retardant situation of the made expansion type flame retardant of table 6 in Vilaterm
| Fire retardant consumption (%), weight | 0 | 20 | 25 | 30 | 32 | 35 |
| UL-94 measures | Stepless | Stepless | V-2 | V-1 | V-1 | V-0 |
Claims (3)
1. the preparation method of polyol ester phosphate and modified polyisocyanate thing is characterized in that this method may further comprise the steps:
(1) with polyvalent alcohol: phosphoric acid=1: the 1.1-1.5 mol ratio feeds intake, and band aqua consumption is 1/4 of a raw material input weight, adds and has whisking appliance, in the reactor drum of TM and reflux exchanger, in temperature 100-160 ℃ of reaction 3-6 hour, obtains polyol ester;
(2) 5-20% of POLYMETHYLENE POLYPHENYLISOCYANATE by carboxylate weight fed intake, add and have whisking appliance, in the reactor drum of TM and reflux exchanger; In temperature 80-120 ℃ of reaction 2-4 hour, obtain the modifier of polyol ester and POLYMETHYLENE POLYPHENYLISOCYANATE;
Wherein, polyvalent alcohol is a terepthaloyl moietie, NSC 6366, USP Kosher, any in TriMethylolPropane(TMP) or the tetramethylolmethane; POLYMETHYLENE POLYPHENYLISOCYANATE is 4,4 '-diphenylmethanediisocyanate, any in tolylene diisocyanate or the many penylenes POLYMETHYLENE POLYPHENYLISOCYANATE; The reaction of step (2) is carried out under catalyst action, and this catalyzer is a diethylenetriamine, triethylene tetramine, polyethylene polyamine, dibutyl tin laurate, any in the stannous octoate.
2. the polyol ester phosphate and the modified polyisocyanate thing that prepare of the preparation method of polyol ester phosphate and modified polyisocyanate thing according to claim 1.
3. be used for the fire-retardant of polyolefine material like said polyol ester phosphate of claim 2 and modified polyisocyanate thing.
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| CN102040744B (en) * | 2010-12-10 | 2012-03-21 | 四川大学 | Mixed salt flame retardant of phosphoric acid, gluconic acid and melamine and preparation method thereof |
| CN102585293B (en) * | 2011-01-14 | 2013-10-16 | 中国林业科学研究院木材工业研究所 | Flame retardant, and preparation method and application thereof |
| CN102924521B (en) * | 2012-10-18 | 2014-11-26 | 四川大学 | Silicon-containing expansive flame retardant and preparation method and application thereof |
| CN103046336A (en) * | 2012-11-06 | 2013-04-17 | 青岛文创科技有限公司 | Phosphor-boron composite flame retardant |
| CN103772640B (en) * | 2014-01-20 | 2015-09-16 | 四川大学 | A kind of flame retardant type wood adhesive and its preparation method and application |
| AR100394A1 (en) * | 2014-05-02 | 2016-10-05 | Dow Global Technologies Llc | PHOSPHATE ADHESION PROMOTERS |
| CN105367604B (en) * | 2015-11-13 | 2017-04-12 | 太原理工大学 | Phosphorus-nitrogen-containing star-type charring agent and preparation method thereof |
| CN107652324B (en) * | 2017-09-22 | 2019-09-24 | 东北林业大学 | Three-source-in-one expansion type fire retardant and its synthetic method and application |
| CN110951042B (en) * | 2019-12-07 | 2021-12-17 | 合众（佛山）化工有限公司 | Oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin and preparation method thereof |
| CN111662328B (en) * | 2020-06-12 | 2021-10-15 | 万华节能科技集团股份有限公司 | Derivative of flame-retardant environment-friendly toluene diisocyanate and synthetic method thereof |
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