CN103665755A - Preparation methods of melamino-formaldehyde resin for foam and melamino-formaldehyde resin foam - Google Patents
Preparation methods of melamino-formaldehyde resin for foam and melamino-formaldehyde resin foam Download PDFInfo
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- CN103665755A CN103665755A CN201310614126.3A CN201310614126A CN103665755A CN 103665755 A CN103665755 A CN 103665755A CN 201310614126 A CN201310614126 A CN 201310614126A CN 103665755 A CN103665755 A CN 103665755A
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Abstract
The invention discloses preparation methods of melamino-formaldehyde resin for foam and melamino-formaldehyde resin foam, wherein the preparation method of melamino-formaldehyde resin for foam comprises the steps as follows: 1), an organic solvent is taken as a solvent, an amine compound is taken as a catalyst, phosphate compounds and polysiloxane compound are taken as raw reaction materials, a phosphorus containing polysiloxane modifying agent is synthesized under the protection of nitrogen, insoluble salts are filtered and removed after the reaction is finished, and the solvent and unreacted objects are removed through reduced pressure distillation, so that the phosphorus containing polysiloxane modifying agent is obtained; and 2), melamine and a formaldehyde solution are put into a reaction kettle in proportion for reaction, the modifying agent in step 1) is added in a mass proportion after the solution becomes clarified, and after the reaction is performed continuously for 0.5-3 hours, the cooling is performed to obtain a product. With the adoption of the melamino-formaldehyde resin foam produced by the modified melamino-formaldehyde resin prepared by the invention, the problem that the flame retardant property is reduced while the toughness of the toughened and modified melamino-formaldehyde resin foam is improved is effectively solved.
Description
Technical field
The present invention relates to the preparation method of terpolycyantoamino-formaldehyde resin for a kind of foam, belong to polymeric material field.
The invention still further relates to a kind of preparation method who uses the terpolycyantoamino-formaldehyde resin foam of terpolycyantoamino-formaldehyde resin based on above-mentioned foam.
Background technology
Melamine foamed plastic is to take terpolycyantoamino-formaldehyde resin as matrix, a kind of flame-retarded foamed plastic making through special foam process.It has excellent flame retardant resistance, thermal insulation, thermostability, sound absorption, safety and sanitation and good secondary workability, can be widely used in the fields such as building, machinery, chemical industry, communications and transportation.
Terpolycyantoamino-formaldehyde resin curing by the realization that is cross-linked with each other of methylene radical or dimethylene ehter bond, because methylene radical two ends are connected with the triazine ring that steric hindrance is very large, and a plurality of methylene radical are with interlaced between triazine ring, so use terpolycyantoamino-formaldehyde resin foam prepared by unmodified terpolycyantoamino-formaldehyde resin to exist fragility large, easy dry linting, the problems such as compressive strength is low, have limited the application of terpolycyantoamino-formaldehyde resin foam.Therefore the flexility that, improves terpolycyantoamino-formaldehyde resin foam is significant for the application of development terpolycyantoamino-formaldehyde resin foam.
In order to improve the fragility of terpolycyantoamino-formaldehyde resin foam, strengthen its application performance, researchist has carried out a large amount of modification experiment work.Patent US3093600 is by improving elasticity and the chip resistance performance of foam, DeGrain with trivalent alcohol.Patent US5162487 is by adding the trimeric cyanamide in hydroxyl alkoxy grp substituted melamine formaldehyde resin, and to increase the flexibility of molecule, effect is not clearly, but this patent is the performance of improving melamino-formaldehyde foam, has pointed out a kind of thinking.Patent CN 101735555A by adding the snappiness that polyol improves terpolycyantoamino-formaldehyde resin foam in terpolycyantoamino-formaldehyde resin performed polymer, yet because the properties-correcting agent adding has increased the combustiblecomponents in terpolycyantoamino-formaldehyde resin foam, must cause the flame retardant properties of terpolycyantoamino-formaldehyde resin foam to decline.Patent CN 102086270 improves tear strength and the tensile property of foam by add alcamine compound in terpolycyantoamino-formaldehyde resin performed polymer, but the flame retardant properties of obtained terpolycyantoamino-formaldehyde resin foam is not analyzed.
The invention discloses and a kind ofly by add phosphorus containing siloxane properties-correcting agent in terpolycyantoamino-formaldehyde resin building-up process, improving the flexible while of terpolycyantoamino-formaldehyde resin foam, do not reduce the flame retardant resistance of terpolycyantoamino-formaldehyde resin foam.The foam that modified melamine-formaldehyde resin prepared by use the present invention is produced has good mechanical property and flame retardant properties.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, proposed the preparation method of terpolycyantoamino-formaldehyde resin for a kind of foam, the foam that modified melamine-formaldehyde resin prepared by employing the present invention is produced has good mechanical property and flame retardant properties.
The present invention is achieved by the following technical solutions:
A foam terpolycyantoamino-formaldehyde resin preparation method, comprises the following steps:
1), properties-correcting agent is synthetic: with an organic solvent make solvent, aminated compounds is catalyzer, phosphate compounds and polysiloxane compounds are reaction raw materials, above-mentioned substance metering are dropped in reactor to synthetic phosphorus containing siloxane properties-correcting agent under nitrogen protection, building-up process temperature of reaction is controlled at 0 ℃ ~ 30 ℃, reaction times 5 ~ 25hr, after reaction finishes, removes by filter insoluble salt, underpressure distillation, except desolventizing and unreacted reactant, obtains phosphorus containing siloxane properties-correcting agent again;
2), the preparation of terpolycyantoamino-formaldehyde resin for foam: the molar ratio of trimeric cyanamide, formaldehyde solution being pressed to 1:1.5 ~ 1:3 drops into reactor, and adding alkali lye, to regulate pH be 8.0 ~ 10.0, be warming up to 60 ℃ ~ 110 ℃, after solution becomes clarification, example adds the described properties-correcting agent of step (1) in mass ratio, cooling after continuation reaction 0.5hr ~ 3hr, obtain water white transparency thick liquid.
In described step (1), organic solvent is one or more in methyl alcohol, ethanol, toluene, dimethylbenzene, hexanaphthene, methylene dichloride, tetrahydrofuran (THF), acetone, ether.
In described step (1), aminated compounds is one or more in monoethylamine, quadrol, triethylamine, phenylethylamine.
In described step (1), phosphate compounds is one or more in tolyl diphenyl phosphoester, phosphenylic acid diethyl ester, phenyldichlorophosphine acid esters, cumyl phosphoric acid ester, Tri-isopropylphenyl phosphate, three (p-nitrophenyl) phosphoric acid ester.
In described step (1), phosphate compounds and aminated compounds mol ratio are between 1:0.5 ~ 1:4.
Described phosphate compounds and aminated compounds mol ratio are preferably controlled between 1:1 ~ 1:3.
Polysiloxane compounds is hydroxyl-terminated injecting two methyl siloxane in described step (1), and this hydroxyl-terminated injecting two methyl siloxane is one or more in the hydroxyl-terminated injecting two methyl siloxane of 4-7 of the polymerization degree.
In described step (1), polysiloxane compounds and aminated compounds mol ratio are between 1:0.5 ~ 1:4.
Described polysiloxane compounds and aminated compounds mol ratio are preferably controlled between 1:1 ~ 1:3.
In described step (1), building-up process temperature of reaction is preferably controlled at 0 ℃ ~ 20 ℃, and the reaction times is preferably controlled at 10 ~ 20hr.
In described step (2), the mol ratio of preferred trimeric cyanamide and formaldehyde is between 1:2 ~ 1:2.5, it is 8.5 ~ 9.5 that hydro-oxidation sodium regulates pH, be warming up to 70 ℃ ~ 100 ℃, after becoming clarification, solution adds the described properties-correcting agent of step (1), cooling after continuation reaction 1hr ~ 2hr, obtain water white transparency thick liquid.
Temperature rise rate is controlled at 1.5 ℃/min ~ 2.5 ℃/min in described step (2).
Described temperature rise rate is preferably controlled at 2 ℃/min.
In described step (2), the quality of properties-correcting agent is 0 ~ 20% of terpolycyantoamino-formaldehyde resin quality.
The quality optimization of described properties-correcting agent is controlled as 0.5 ~ 10% of terpolycyantoamino-formaldehyde resin quality.
another technical purpose of the present invention is to providethe preparation method of the terpolycyantoamino-formaldehyde resin foam of terpolycyantoamino-formaldehyde resin for a kind of above-mentioned foam, be specially: after for foam, terpolycyantoamino-formaldehyde resin, Sodium dodecylbenzene sulfonate, Skellysolve A, formic acid mix, in microwave, foamable is 60 seconds, can obtain terpolycyantoamino-formaldehyde resin foam; The described mass fraction of terpolycyantoamino-formaldehyde resin, Sodium dodecylbenzene sulfonate, Skellysolve A, formic acid for foam is followed successively by: 100,3,8,6; Terpolycyantoamino-formaldehyde resin foam obtains parameter: foam density is 8.1 ~ 11.5kg/m
3, drawing high intensity is 0.087kPa ~ 0.126kPa, oxygen index is 32.3 ~ 37.1
beneficial effect
The present invention is for the preparation of foam terpolycyantoamino-formaldehyde resin, and the foam that uses modified melamine-formaldehyde resin prepared by the present invention to produce efficiently solves the melamino-formaldehyde foam problem that flame retardant properties reduces when toughness improves of toughening modifying.
Embodiment
The embodiment of the present invention given below, is just further described specifically the present invention.It is important to point out, embodiment, only for the present invention is further elaborated, can not be interpreted as limiting the scope of the invention.The present embodiment is done to appropriate improvement or change, still belong to protection scope of the present invention.
Embodiment 1
1), the preparation of properties-correcting agent: dry tetrahydrofuran 1L and 211g phenyldichlorophosphine acid esters are added in the reactor with thermometer, agitator, drying installation and nitrogen protection; start agitator; and temperature is down to 0 ℃; after phenyldichlorophosphine acid esters dissolves, add 212g triethylamine (phenyldichlorophosphine acid esters and triethylamine mol ratio are 1:2.1), continue to stir 20min.Hydroxyl-terminated injecting two methyl siloxane (polymerization degree is 4) 672g is dissolved in to (hydroxyl-terminated injecting two methyl siloxane and triethylamine mol ratio are 1:1) in 1L dry tetrahydrofuran, and solution is added in aforesaid reaction vessel to successive reaction 4hr.Post-heating is to room temperature, stirring reaction 10hr, and reaction solution is gone out triethylamine hydrochloride by filtration unit, then underpressure distillation is except desolventizing and unreacted reactant, obtains water white transparency thick liquid, is properties-correcting agent.
2), the preparation of terpolycyantoamino-formaldehyde resin for foam: by 37% industrial formaldehyde solution 1250g, add with thermometer, in the reactor of agitator and reflux exchanger, start stirring, in room temperature, with sodium hydroxide, regulate pH=8.0, adding trimeric cyanamide 950g(trimeric cyanamide and formaldehyde mole ratio is 1:2 again), by 2 ℃/min heat-up rate, be raised to 90 ℃ of reactions, question response liquid become that to add properties-correcting agent 30g(properties-correcting agent consumption after clarification be trimeric cyanamide consumption 3.2%), cooling after continuation reaction 1hr, obtain water white transparency thick liquid, be the foam terpolycyantoamino-formaldehyde resin through modification.
By above-mentioned synthetic resins 100g, add Sodium dodecylbenzene sulfonate 3g, Skellysolve A 8g, formic acid 6g, in microwave, foamable is 60 seconds, obtains terpolycyantoamino-formaldehyde resin foam, and foam density is 8.1kg/m
3, tensile strength is 0.087 kPa, oxygen index is 32.3.
Embodiment 2
1), the preparation of properties-correcting agent: dry dimethylbenzene 1.2L and 446g tolyl diphenyl phosphoester are added in the reactor with thermometer, agitator, drying installation and nitrogen protection; start agitator; and temperature is down to 0 ℃; after tolyl diphenyl phosphoester dissolves, add 153g diethylamine (tolyl diphenyl phosphoester and diethylamine mol ratio are 1:1.6), continue to stir 20min.Hydroxyl-terminated injecting two methyl siloxane (polymerization degree is 5) 700g is dissolved in the dry dimethylbenzene of 1L (hydroxyl-terminated injecting two methyl siloxane and diethylamine mol ratio are 1:1.2), and solution is added in aforesaid reaction vessel to successive reaction 4hr.Post-heating is to room temperature, stirring reaction 10hr, and reaction solution is gone out diethylamine hydrochloride by filtration unit, then underpressure distillation is except desolventizing and unreacted reactant, obtains water white transparency thick liquid, is properties-correcting agent.
2), the preparation of terpolycyantoamino-formaldehyde resin for foam: by 37% industrial formaldehyde solution 1250g, add with thermometer, in the reactor of agitator and reflux exchanger, start stirring, in room temperature, with sodium hydroxide, regulate pH=8.0, adding trimeric cyanamide 920g(trimeric cyanamide and formaldehyde mole ratio is 1:2.1 again), by 2 ℃/min heat-up rate, be raised to 90 ℃ of reactions, question response liquid adds properties-correcting agent 50g (properties-correcting agent consumption is 5.4% of trimeric cyanamide consumption) after becoming clarification, cooling after continuation reaction 1hr, obtain water white transparency thick liquid, be the foam terpolycyantoamino-formaldehyde resin through modification.
By above-mentioned synthetic resins 100g, add Sodium dodecylbenzene sulfonate 3g, Skellysolve A 8g, formic acid 6g, in microwave, foamable is 60 seconds, obtains terpolycyantoamino-formaldehyde resin foam, and foam density is 9.3kg/m
3, tensile strength is 0.098 kPa, oxygen index is 34.1.
Embodiment 3
1), the preparation of properties-correcting agent: dry methylene chloride 1L and 181g phosphenylic acid diethyl ester are added in the reactor with thermometer, agitator, drying installation and nitrogen protection; start agitator; and temperature is down to 0 ℃; after phosphenylic acid diethyl ester dissolves, add 254g phenylethylamine (phosphenylic acid diethyl ester and phenylethylamine mol ratio are 1:2.3), continue to stir 20min.Hydroxyl-terminated injecting two methyl siloxane (polymerization degree is 6) 672g is dissolved in to (hydroxyl-terminated injecting two methyl siloxane and phenylethylamine mol ratio are 1:1.5) in 1L dry methylene chloride, and solution is added in aforesaid reaction vessel to successive reaction 4hr.Post-heating is to room temperature, stirring reaction 10hr, and reaction solution is removed phenylethylamine hydrochloride by filtration unit, then underpressure distillation is except desolventizing and unreacted reactant, obtains water white transparency thick liquid, is properties-correcting agent.
2), the preparation of terpolycyantoamino-formaldehyde resin for foam: by 37% industrial formaldehyde solution 1250g, add with thermometer, in the reactor of agitator and reflux exchanger, start stirring, in room temperature, with sodium hydroxide, regulate pH=8.0, adding trimeric cyanamide 878g(trimeric cyanamide and formaldehyde mole ratio is 1:2.2 again), by 2 ℃/min heat-up rate, be raised to 90 ℃ of reactions, question response liquid become that to add properties-correcting agent 70g(properties-correcting agent consumption after clarification be trimeric cyanamide consumption 8.0%), cooling after continuation reaction 1hr, obtain water white transparency thick liquid, be the foam terpolycyantoamino-formaldehyde resin through modification.
By 100 parts of above-mentioned synthetic resins, add 3 parts of Sodium dodecylbenzene sulfonatees, 8 parts of Skellysolve As, 6 parts, formic acid, in microwave, foamable is 60 seconds, obtains terpolycyantoamino-formaldehyde resin foam, and foam density is 10.2kg/m
3, tensile strength is 0.113 kPa, oxygen index is 36.4.
Embodiment 4
1), the preparation of properties-correcting agent: dry toluene 1.5L and 499g Tri-isopropylphenyl phosphate are added in the reactor with thermometer, agitator, drying installation and nitrogen protection; start agitator; and temperature is down to 0 ℃; after Tri-isopropylphenyl phosphate dissolves, add 94g monoethylamine (Tri-isopropylphenyl phosphate and monoethylamine mol ratio are 1:1.9), continue to stir 20min.Hydroxyl-terminated injecting two methyl siloxane (polymerization degree is 7) 1176g is dissolved in to (hydroxyl-terminated injecting two methyl siloxane and monoethylamine mol ratio are 1:1) in 1.5L dry toluene, and solution is added in aforesaid reaction vessel to successive reaction 4hr.Post-heating is to room temperature, stirring reaction 10hr, and reaction solution is removed monoethylamine hydrochloride by filtration unit, then underpressure distillation goes out desolventizing and unreacted reactant, obtains water white transparency thick liquid, is properties-correcting agent.
2), the preparation of terpolycyantoamino-formaldehyde resin for foam: by 37% industrial formaldehyde solution 1250g, add with thermometer, in the reactor of agitator and reflux exchanger, start stirring, in room temperature, with sodium hydroxide, regulate pH=8.0, adding trimeric cyanamide 792g(trimeric cyanamide and formaldehyde mole ratio is 1:2.4 again), by 2 ℃/min heat-up rate, be raised to 90 ℃ of reactions, question response liquid become that to add properties-correcting agent 79g(properties-correcting agent consumption after clarification be trimeric cyanamide consumption 10.0%), cooling after continuation reaction 1hr, obtain water white transparency thick liquid, be the foam terpolycyantoamino-formaldehyde resin through modification.
By 100 parts of above-mentioned synthetic resins, add 3 parts of Sodium dodecylbenzene sulfonatees, 8 parts of Skellysolve As, 6 parts, formic acid, in microwave, foamable is 60 seconds, obtains terpolycyantoamino-formaldehyde resin foam, and foam density is 11.5kg/m
3, tensile strength is 0.126 kPa, oxygen index is 37.1.
Claims (16)
1. a foam terpolycyantoamino-formaldehyde resin preparation method, is characterized in that, described foam comprises the following steps by the preparation process of terpolycyantoamino-formaldehyde resin:
1), properties-correcting agent is synthetic: with an organic solvent make solvent, aminated compounds is catalyzer, phosphate compounds and polysiloxane compounds are reaction raw materials, above-mentioned substance metering are dropped in reactor to synthetic phosphorus containing siloxane properties-correcting agent under nitrogen protection, building-up process temperature of reaction is controlled at 0 ℃ ~ 30 ℃, reaction times 5 ~ 25hr, after reaction finishes, removes by filter insoluble salt, underpressure distillation, except desolventizing and unreacted reactant, obtains phosphorus containing siloxane properties-correcting agent again;
2), the preparation of terpolycyantoamino-formaldehyde resin for foam: the molar ratio of trimeric cyanamide, formaldehyde solution being pressed to 1:1.5 ~ 1:3 drops into reactor, and adding alkali lye, to regulate pH be 8.0 ~ 10.0, be warming up to 60 ℃ ~ 110 ℃, after solution becomes clarification, example adds the described properties-correcting agent of step (1) in mass ratio, cooling after continuation reaction 0.5hr ~ 3hr, obtain water white transparency thick liquid.
2. a kind of foam terpolycyantoamino-formaldehyde resin preparation method according to claim 1, is characterized in that: in described step (1), organic solvent is one or more in methyl alcohol, ethanol, toluene, dimethylbenzene, hexanaphthene, methylene dichloride, tetrahydrofuran (THF), acetone, ether.
3. a kind of foam terpolycyantoamino-formaldehyde resin preparation method according to claim 1, is characterized in that: in described step (1), aminated compounds is one or more in monoethylamine, quadrol, triethylamine, phenylethylamine.
4. a kind of foam terpolycyantoamino-formaldehyde resin preparation method according to claim 1, is characterized in that: in described step (1), phosphate compounds is one or more in tolyl diphenyl phosphoester, phosphenylic acid diethyl ester, phenyldichlorophosphine acid esters, cumyl phosphoric acid ester, Tri-isopropylphenyl phosphate, three (p-nitrophenyl) phosphoric acid ester.
5. a kind of foam terpolycyantoamino-formaldehyde resin preparation method according to claim 1, is characterized in that: in described step (1), phosphate compounds and aminated compounds mol ratio are between 1:0.5 ~ 1:4.
6. a kind of foam terpolycyantoamino-formaldehyde resin preparation method according to claim 5, is characterized in that: described phosphate compounds and aminated compounds mol ratio are preferably controlled between 1:1 ~ 1:3.
7. a kind of foam terpolycyantoamino-formaldehyde resin preparation method according to claim 1, it is characterized in that: polysiloxane compounds is hydroxyl-terminated injecting two methyl siloxane in described step (1), this hydroxyl-terminated injecting two methyl siloxane is one or more in the hydroxyl-terminated injecting two methyl siloxane of 4-7 of the polymerization degree.
8. a kind of foam terpolycyantoamino-formaldehyde resin preparation method according to claim 1, is characterized in that: in described step (1), polysiloxane compounds and aminated compounds mol ratio are between 1:0.5 ~ 1:4.
9. a kind of foam terpolycyantoamino-formaldehyde resin preparation method according to claim 8, is characterized in that: described polysiloxane compounds and aminated compounds mol ratio are preferably controlled between 1:1 ~ 1:3.
10. a kind of foam terpolycyantoamino-formaldehyde resin preparation method according to claim 1, is characterized in that: in described step (1), building-up process temperature of reaction is preferably controlled at 0 ℃ ~ 20 ℃, and the reaction times is preferably controlled at 10 ~ 20hr.
The preparation method of terpolycyantoamino-formaldehyde resin for 11. a kind of foams according to claim 1, it is characterized in that: in described step (2), the mol ratio of preferred trimeric cyanamide and formaldehyde is between 1:2 ~ 1:2.5, it is 8.5 ~ 9.5 that hydro-oxidation sodium regulates pH, be warming up to 70 ℃ ~ 100 ℃, after becoming clarification, solution adds the described properties-correcting agent of step (1), cooling after continuation reaction 1hr ~ 2hr, obtain water white transparency thick liquid.
The preparation method of terpolycyantoamino-formaldehyde resins for 12. a kind of foams according to claim 1, is characterized in that: in described step (2), temperature rise rate is controlled at 1.5 ℃/min ~ 2.5 ℃/min.
The preparation method of terpolycyantoamino-formaldehyde resin for 13. a kind of foams according to claim 12, is characterized in that: described temperature rise rate is preferably controlled at 2 ℃/min.
The preparation method of terpolycyantoamino-formaldehyde resin for 14. a kind of foams according to claim 1, is characterized in that: in described step (2), the quality of properties-correcting agent is 0 ~ 20% of terpolycyantoamino-formaldehyde resin quality.
The preparation method of terpolycyantoamino-formaldehyde resin for 15. a kind of foams according to claim 14, is characterized in that: the quality optimization of described properties-correcting agent is controlled as 0.5 ~ 10% of terpolycyantoamino-formaldehyde resin quality.
16. 1 kinds of preparation methods that use the terpolycyantoamino-formaldehyde resin foam of terpolycyantoamino-formaldehyde resin based on foam claimed in claim 1, it is characterized in that: after for foam, terpolycyantoamino-formaldehyde resin, Sodium dodecylbenzene sulfonate, Skellysolve A, formic acid mix, in microwave, foamable is 60 seconds, can obtain terpolycyantoamino-formaldehyde resin foam; The described mass fraction of terpolycyantoamino-formaldehyde resin, Sodium dodecylbenzene sulfonate, Skellysolve A, formic acid for foam is followed successively by: 100,3,8,6; Terpolycyantoamino-formaldehyde resin foam obtains parameter: foam density is 8.1 ~ 11.5kg/m
3, drawing high intensity is 0.087kPa ~ 0.126kPa, oxygen index is 32.3 ~ 37.1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106366268A (en) * | 2016-08-31 | 2017-02-01 | 张进红 | Phosphate modified melamine flame-retarding sound absorption foam material for crane and preparation method of phosphate modified melamine flame-retarding sound absorption foam material |
| CN106832164A (en) * | 2017-02-27 | 2017-06-13 | 天津市居安泰科技有限公司 | A kind of rigid foam preparation method of tripolycyanamide amino resin |
| CN106832762A (en) * | 2017-02-27 | 2017-06-13 | 天津市居安泰科技有限公司 | A kind of preparation method of low-density flame melamine formaldehyde resin rigid foam |
| CN106967275A (en) * | 2016-01-13 | 2017-07-21 | 华东理工大学 | A kind of preparation method of fire-retardant heat insulation two-component modified melamine-formaldehyde cystosepiment |
| CN107892738A (en) * | 2017-05-16 | 2018-04-10 | 中国科学院成都有机化学有限公司 | A kind of hydrophobic melamine foam resin dedicated liquid, preparation method and expanding foam solution prepared therefrom |
| CN109438642A (en) * | 2018-11-19 | 2019-03-08 | 中国科学院成都有机化学有限公司 | A kind of combustibility A grades melamine foamed plastic and preparation method thereof |
| CN116637566A (en) * | 2023-07-27 | 2023-08-25 | 潍坊万丰新材料科技有限公司 | Preparation method of microencapsulated flame retardant |
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| CN106967275A (en) * | 2016-01-13 | 2017-07-21 | 华东理工大学 | A kind of preparation method of fire-retardant heat insulation two-component modified melamine-formaldehyde cystosepiment |
| CN106967275B (en) * | 2016-01-13 | 2019-04-05 | 华东理工大学 | A kind of preparation method of fire-retardant heat insulation two-component modified melamine-formaldehyde cystosepiment |
| CN106366268A (en) * | 2016-08-31 | 2017-02-01 | 张进红 | Phosphate modified melamine flame-retarding sound absorption foam material for crane and preparation method of phosphate modified melamine flame-retarding sound absorption foam material |
| CN106832164A (en) * | 2017-02-27 | 2017-06-13 | 天津市居安泰科技有限公司 | A kind of rigid foam preparation method of tripolycyanamide amino resin |
| CN106832762A (en) * | 2017-02-27 | 2017-06-13 | 天津市居安泰科技有限公司 | A kind of preparation method of low-density flame melamine formaldehyde resin rigid foam |
| CN106832164B (en) * | 2017-02-27 | 2019-11-08 | 天津市居安泰科技有限公司 | A kind of preparation method of rigid foam tripolycyanamide amino resin |
| CN107892738A (en) * | 2017-05-16 | 2018-04-10 | 中国科学院成都有机化学有限公司 | A kind of hydrophobic melamine foam resin dedicated liquid, preparation method and expanding foam solution prepared therefrom |
| CN107892738B (en) * | 2017-05-16 | 2019-10-15 | 中国科学院成都有机化学有限公司 | A kind of resin dedicated liquid of hydrophobic melamine foam, preparation method and expanding foam solution prepared therefrom |
| CN109438642A (en) * | 2018-11-19 | 2019-03-08 | 中国科学院成都有机化学有限公司 | A kind of combustibility A grades melamine foamed plastic and preparation method thereof |
| CN116637566A (en) * | 2023-07-27 | 2023-08-25 | 潍坊万丰新材料科技有限公司 | Preparation method of microencapsulated flame retardant |
| CN116637566B (en) * | 2023-07-27 | 2023-10-13 | 潍坊万丰新材料科技有限公司 | Preparation method of microencapsulated flame retardant |
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