CN103755956A - Preparation method for green flame retardant rigid polyurethane-imide foamed plastic - Google Patents
Preparation method for green flame retardant rigid polyurethane-imide foamed plastic Download PDFInfo
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Abstract
Belonging to the field of environmental friendly high polymer materials, the invention relates to a preparation method for a green flame retardant rigid polyurethane-imide foamed plastic. The foamed plastic comprises the following raw materials by weight: 100 parts of polyether polyol, 180-200 parts of polyisocyanate, 10-20 parts of 3, 3', 4, 4',-benzophenone tetracid dianhydride, 5-10 parts of zinc borate, 2-5 parts of kaolin, 2-5 parts of hollow glass microspheres, 0.2-0.25 part of water, 0.8-1.0 part of n-pentane, 0.04-0.06 part of triethanolamine, 0.06-0.08 part of stannous octoate, 0.3-0.5 part of diethanol methyl ether, and 0.2-0.25 part of dimethyl silicon oil. The preparation method includes: firstly preparing an inorganic composite flame retardant, a polyimide prepolymer, then conducting mixing with polyether polyol, and performing foaming and curing. The product prepared by the invention has good flame retardant properties, and can be applied to various heat insulation fields and the packaging industry.
Description
Technical field
The invention belongs to environment-friendly polymers preparation field, be specifically related to a kind of preparation method of Green Flammability hard polyaminoester-acid imide foam plastics.
Background technology
Hard polyaminoester-imide (Polyurethane-imide, be called for short PUI) porous plastics is that urethane (PU) porous plastics and polyimide (PI) porous plastics interpenetrate, cross development and the novel high polymer engineering materials that forms.
This segmented copolymer can form good microphase-separated feature, both kept the agent structure of soft, hard section of urethane, newly form again this nitrogen heterocyclic rigid radical of imide, avoided the temperature tolerance of urethane poor, the shortcoming such as the workability of facile hydrolysis and polyimide is poor.Due to cell texture, density is lower, has accelerated scattering and disappearing of combustionvelocity and quality, so hard polyaminoester-acid imide foam flame retardant of plastic poor-performing, the oxygen index of its burning, between 20～25, produces a large amount of toxic smogs, very easily causes people's death by suffocation.
Hard polyaminoester-acid imide foam plastics that flame retardant properties is good are met little fire and can certainly be put out, not fire hazardous; In fire, the danger that can reduce fire spread and produce pungency toxic smog.By adding various fire retardants, realize raising hard polyaminoester-acid imide foam flame retardant of plastic at present.Fire retardant is divided into additive flame retardant and the large class of reactive flame retardant two, and wherein most fire retardants all contains halogen and phosphorus element.In general, some are through hard polyaminoester-acid imide foam plastics of fire-retardant finish, although fire-retardant rank is improved, the smoke-producing amount of system and product smoke toxicity often increase.In recent years, people recognize serious harm halogen-containing and that phosphorus element fire retardant causes environmental and biological materials day by day.Halogen-containing and phosphorus element fire retardant is emitted when burning poisonous and sour gas, cigarette, people is suffocated and damage equipment, and in aquatic bird, fish, marine mammal, Wildlife and tissue, all have polybromodiphenyl ether, and amount increases just year by year.Under this background, the research and development of halogen and phosphorus element fire retardant are significant, and wherein composite inorganic fire retardant system is one of substitute of halogen system and phosphorus flame retardant.
The present invention utilizes super-refinement, micro encapsulation, fire retardant compounded technology to prepare environmentally friendly composite inorganic fire retardant, in the situation that composite inorganic fire retardant usage quantity is less, guarantee that hard polyaminoester-acid imide foam plastics have excellent flame retardant properties, smoke suppressing and mechanical property, and reach the object that reduces cost.The inventive method is simple, be easy to suitability for industrialized production, can meet building, and refrigeration equipment is decorated the requirement of the industries such as household electrical appliance.
Summary of the invention
The object of the invention is to have overcome prior art deficiency, by the synergy of nano-zinc borate, kaolin and hollow glass microbead, improve hard polyaminoester-acid imide foam flame retardant of plastic performance, a kind of preparation method of Green Flammability hard polyaminoester-acid imide foam plastics with good flame-retardance energy, smoke suppressing and mechanical property is provided.
Technical scheme of the present invention and technical characterictic are:
The present invention is a kind of preparation method of Green Flammability hard polyaminoester-acid imide foam plastics, the weight proportion that it is characterized in that raw material and raw material is: 100 parts of polyether glycols, 180～200 parts of polyisocyanates, 3,3 ', 4,4 ', 10～20 parts of-benzophenone tetracarboxylic dianhydrides, 5～10 parts of zinc borates, 2～5 parts of kaolin, 2～5 parts of hollow glass microballoons, 0.2～0.25 part, water, 0.8～1.0 part of Skellysolve A, 0.04～0.06 part of trolamine, 0.06～0.08 part of stannous octoate, 0.3～0.5 part of di-alcohol methyl ether, 0.2～0.25 part of dimethyl silicone oil.
The preparation method of this matrix material is:
(1) preparation of composite inorganic fire retardant: prepare certain density titanate coupling agent solution with organic solvent, then add the nano-zinc borate of certain mass, above-mentioned solution is carried out to ultrasonic dispersion, in thermostat water bath, react for some time, through suction filtration, vacuum-drying, grinding, sieve, obtain the nano-zinc borate powder of surface modification.Intercalator potassium acetate and kaolin are placed on to natural deliquescence in mortar, grind for some time, through suction filtration, vacuum-drying, grinding, sieve, obtain the kaolin powder of potassium acetate intercalation modifying.Hollow glass microbead is distributed in polyoxyethylene glycol raw material, then respectively the polyoxyethylene glycol that contains hollow glass microbead and isocyanic ester are dispersed in emulsion, carry out interfacial polymerization, through suction filtration, vacuum-drying, grinding, sieve, obtaining polyurethane elastomer is cyst wall, and hollow glass microballoon is the microcapsule particle of the capsule heart.Zinc borate after modification, kaolin and hollow glass microballoon are carried out in star-like ball mill to dry mixed, mixing time is 2～5h, and rotating speed is 200～500r/min, obtains inorganic composite flame retardants;
(2) preparation of polyimide prepolymer: at room temperature prepare 3,3 ', 4,4 ', the N of-benzophenone tetracarboxylic dianhydride, N ' ,-dimethyl formamide saturated solution, again polyisocyanates and saturated solution are reacted under oil bath heated and stirred, temperature of reaction is 60～80 ℃, and the reaction times is 20～30min, and rotating speed is 1500～2000r/min, then temperature is increased to 120～130 ℃, N
2protection, the reaction times is 10～15min, and rotating speed is 1000～1500r/min, and the standing 2～3h of cool to room temperature obtains polyimide prepolymer;
(3) preparation of hard polyaminoester-acid imide foam plastics: inorganic composite flame retardants, water, Skellysolve A, trolamine, stannous octoate, di-alcohol methyl ether, dimethyl silicone oil are mixed according to its weight proportion with polyether glycol, then with after polyimide prepolymer rapid stirring pour in preset mould and foam, wherein mold preheating temperature is 30～40 ℃, foamed time is 5～10min, finally foam materials is put into and in vacuum drying oven, carries out slaking, 90～100 ℃ of curing temperatures, curing time 12h.
The technical requirements of embodiment of the present invention material therefor is as follows.
3,3 ', 4,4 ' ,-benzophenone tetracarboxylic dianhydride (BTDA), purity >=99.5%;
Polymeric MDI, PM-200 (NCO%:30.2～32.0%);
Polyether glycol, 4110 (hydroxyl values: 430 ± 30);
Polyoxyethylene glycol, 400;
Nano-zinc borate, particle diameter≤1.6 μ m;
Kaolin, particle diameter≤2.6 μ m;
Hollow glass microbead, 5～10 μ m;
Coupling agent: titanate coupling agent TM-48, TM-38, silane resin acceptor kh-550, KH-570, analytical pure;
Intercalator: potassium acetate, analytical pure;
Emulsifying agent: Sodium dodecylbenzene sulfonate, analytical pure;
Whipping agent: Skellysolve A, analytical pure:
Linking agent: ethylene glycol monomethyl ether, analytical pure;
Catalyzer: trolamine, analytical pure; Stannous octoate, analytical pure;
Suds-stabilizing agent: dimethyl silicone oil, analytical pure;
Organic solvent: DMF, analytical pure.
Green Flammability type hard polyaminoester-acid imide foam plastics of the present invention, with respect to prior art, have following features:
1, the present invention is using hard polyaminoester-acid imide foam plastics as body material, by the synergy of zinc borate, kaolin and hollow glass microbead, improve the flame retardant properties of rigid foam, finally under less composite inorganic fire retardant, there are excellent flame retardant properties, smoke suppressing and mechanical property hard polyaminoester-acid imide foam plastics.
2, Green Flammability hard foam of the present invention, has application prospect comparatively widely; Its preparation method is simple, and operator can comparatively fast grasp.
Embodiment
The following examples are to further illustrate of the present invention, rather than limit the scope of the invention.
Embodiment 1
(1) take 5～8 parts of dry zinc borates, join in 50mL Virahol, ultrasonic wave is disperseed 15～20min, a certain amount of titanate coupling agent TM-48 is dissolved in 10mL Virahol, at 50 ℃ with magnetic stirrer 15～20min.Mix above-mentioned two kinds of solution, ultrasonic wave is disperseed 20～25min, 90 ℃ of ultrasonic temperature, and then linked reaction for some time in the thermostat water bath of 90 ℃, suction filtration, vacuum-drying, grinding is sieved, and obtains the zinc borate of surface modification.Titanate coupling agent of the present invention, except TM-48, also needs the use that proportions of the titanate coupling agent suitable with other and silane coupling agent, as TM-38, KH-550, KH-570 etc., can carry out surface treatment to zinc borate, meets technique service requirements.
(2) take 2～3 parts of intercalator potassium acetates and 1～2 part of kaolin is placed on natural deliquescence 12h in mortar, grind 5h, with suction filtration after absolute ethanol washing three times, 80 ℃ of vacuum-drying 12h, then grind 200 mesh sieves, obtained the kaolin powder of potassium acetate intercalation modifying.
(3) sodium dodecyl benzene sulfonate aqueous solution of configuration concentration 1～2% first, taking 2～3 parts of hollow glass microbeads is distributed in polyoxyethylene glycol raw material, then the polyoxyethylene glycol that respectively 10～15ml is contained to hollow glass microbead and 15～20ml isocyanic ester are dispersed in emulsion, mix above-mentioned two kinds of solution, ultrasonic wave is disperseed 10～15min, and ultrasonic temperature 50 C carries out interfacial polymerization in electric stirring, stirring velocity 1000～1500r/min, 50～80 ℃ of whipping temps.Through suction filtration, 80 ℃ of vacuum-drying 12h, then ground 200 mesh sieves, obtaining polyurethane elastomer is cyst wall, hollow glass microballoon is the microcapsule particle of the capsule heart.
(4) take respectively 100 parts of kaolin after zinc borate, the 100 parts of modifications after modification and the hollow glass microballoon after 100 parts of modifications and in star-like ball mill, carry out dry mixed, mixing time is 2～5h, rotating speed is 200～500r/min, obtains inorganic composite flame retardants;
(5) preparation of polyimide prepolymer: first take 1 part after processed, at N, N ', prepares in-solvent dimethylformamide.Take 10～15 parts of polyisocyanates, with 3,3 ', 4,4 ',-benzophenone tetracarboxylic dianhydride saturated solution joins in oil bath magnetic stirring apparatus simultaneously and reacts, and temperature of reaction is 60～80 ℃, and the reaction times is 20～30min, rotating speed is 1500～2000r/min, then temperature is increased to 120～130 ℃, the reaction times is 10～15h, N
2protection, rotating speed is 1000～1500r/min, the standing 2～3h of cool to room temperature obtains polyimide prepolymer.According to relevant criterion, the structure of polyimide prepolymer is characterized.
(6) preparation of hard polyaminoester-acid imide foam plastics: take 100 parts of polyether glycols, 5～10 parts of inorganic composite flame retardants, mix according to weight proportion with water, Skellysolve A, trolamine, stannous octoate, di-alcohol methyl ether and dimethyl silicone oil, then with after prefabricated polyimide prepolymer solution rapid stirring pour in preset mould and foam, wherein mold preheating temperature is 30～40 ℃, foamed time is 5～10min, finally foam materials is put into and in vacuum drying oven, carries out slaking, 80～100 ℃ of curing temperatures, curing time 12h.According to relevant criterion, matrix material is carried out to structural characterization and performance test.
(7) will after Green Flammability hard polyaminoester-acid imide foam plastics sample preparation of preparation, by taper calorimeter and oxygen index instrument, carry out flame retardant properties and smoke suppressing sign, analytical results shows, the oxygen index (25～30) of hard polyaminoester-acid imide foam plastics increases compared with rigid urethane foam (15～20), and the amount of being fuming reduces 10%.Adopt hard polyaminoester-acid imide foam plastics of preparing of the present invention compared with rigid urethane foam, its compressive strength improves 20%, composite inorganic fire retardant add the obvious mechanical property of improving hard polyaminoester-acid imide foam plastics.
Embodiment 2
(1) take 5～8 parts of dry zinc borates, join in 50mL Virahol, ultrasonic wave is disperseed 15～20min, a certain amount of titanate coupling agent TM-48 is dissolved in 10mL Virahol, at 50 ℃ with magnetic stirrer 15～20min.Mix above-mentioned two kinds of solution, ultrasonic wave is disperseed 20～25min, 90 ℃ of ultrasonic temperature, and then linked reaction for some time in the thermostat water bath of 90 ℃, suction filtration, vacuum-drying, grinding is sieved, and obtains the zinc borate of surface modification.Titanate coupling agent of the present invention, except TM-48, also needs the use that proportions of the titanate coupling agent suitable with other and silane coupling agent, as TM-38, KH-550, KH-570 etc., can carry out surface treatment to zinc borate, meets technique service requirements.
(2) take 2～3 parts of intercalator potassium acetates and 1～2 part of kaolin is placed on natural deliquescence 12h in mortar, grind 5h, with suction filtration after absolute ethanol washing three times, 80 ℃ of vacuum-drying 12h, then grind 200 mesh sieves, obtained the kaolin powder of potassium acetate intercalation modifying.
(3) sodium dodecyl benzene sulfonate aqueous solution of configuration concentration 1～2% first, taking 2～3 parts of hollow glass microbeads is distributed in polyoxyethylene glycol raw material, then the polyoxyethylene glycol that respectively 10～15ml is contained to hollow glass microbead and 15～20ml isocyanic ester are dispersed in emulsion, mix above-mentioned two kinds of solution, ultrasonic wave is disperseed 10～15min, and ultrasonic temperature 50 C carries out interfacial polymerization in electric stirring, stirring velocity 1000～1500r/min, 50～80 ℃ of whipping temps.Through suction filtration, 80 ℃ of vacuum-drying 12h, then ground 200 mesh sieves, obtaining polyurethane elastomer is cyst wall, hollow glass microballoon is the microcapsule particle of the capsule heart.
(4) take respectively 100 parts of kaolin after zinc borate, the 50 parts of modifications after modification and the hollow glass microballoon after 150 parts of modifications and in star-like ball mill, carry out dry mixed, mixing time is 2～5h, rotating speed is 200～500r/min, obtains inorganic composite flame retardants;
(5) preparation of polyimide prepolymer: first take 1 part after processed, at N, N ', prepares in-solvent dimethylformamide.Take 10～15 parts of polyisocyanates, with 3,3 ', 4,4 ',-benzophenone tetracarboxylic dianhydride saturated solution joins in oil bath magnetic stirring apparatus simultaneously and reacts, and temperature of reaction is 60～80 ℃, and the reaction times is 20～30min, rotating speed is 1500～2000r/min, then temperature is increased to 120～130 ℃, the reaction times is 10～15h, N
2protection, rotating speed is 1000～1500r/min, the standing 2～3h of cool to room temperature obtains polyimide prepolymer.According to relevant criterion, the structure of polyimide prepolymer is characterized.
(6) preparation of hard polyaminoester-acid imide foam plastics: take 100 parts of polyether glycols, 15～20 parts of inorganic composite flame retardants, mix according to weight proportion with water, Skellysolve A, trolamine, stannous octoate, di-alcohol methyl ether and dimethyl silicone oil, then with after prefabricated polyimide prepolymer solution rapid stirring pour in preset mould and foam, wherein mold preheating temperature is 30～40 ℃, foamed time is 5～10min, finally foam materials is put into and in vacuum drying oven, carries out slaking, 80～100 ℃ of curing temperatures, curing time 12h.According to relevant criterion, matrix material is carried out to structural characterization and performance test.
(7) will after Green Flammability hard polyaminoester-acid imide foam plastics sample preparation of preparation, by taper calorimeter and oxygen index instrument, carry out flame retardant properties and smoke suppressing sign, analytical results shows, the oxygen index (30～35) of hard polyaminoester-acid imide foam plastics increases compared with rigid urethane foam (15～20), and the amount of being fuming reduces 30%.Adopt hard polyaminoester-acid imide foam plastics of preparing of the present invention compared with rigid urethane foam, its compressive strength improves 5%, composite inorganic fire retardant add the mechanical property of having improved hard polyaminoester-acid imide foam plastics.
Claims (9)
1. the present invention is a kind of preparation method of Green Flammability hard polyaminoester-acid imide foam plastics, it is characterized in that raw materials used and weight proportion is: 100 parts of polyether glycols, 180～200 parts of polyisocyanates, 3, 3 ', 4, 4 ', 10～20 parts of-benzophenone tetracarboxylic dianhydrides, 5～10 parts of zinc borates, 2～5 parts of kaolin, 2～5 parts of hollow glass microballoons, 0.2～0.25 part, water, 0.8～1.0 part of Skellysolve A, 0.04～0.06 part of trolamine, 0.06～0.08 part of stannous octoate, 0.3～0.5 part of di-alcohol methyl ether, 0.2～0.25 part of dimethyl silicone oil, the preparation of these Green Flammability hard polyaminoester-acid imide foam plastics comprises the following steps: inorganic composite flame retardants preparation, the preparation of polyimide prepolymer, the foaming slaking of Green Flammability hard polyaminoester-acid imide foam plastics.
2. the preparation method of Green Flammability hard polyaminoester-acid imide foam plastics as claimed in claim 1, is characterized in that hydroxyl value >=400 of raw materials used polyether glycol (4110).
3. the preparation method of Green Flammability hard polyaminoester-acid imide foam plastics as claimed in claim 1, it is characterized in that NCO% >=32.0% of raw materials used polyisocyanates (PM-200), the mass ratio of polyisocyanates and polyether glycol is 180%～200%.
4. the preparation method of Green Flammability hard polyaminoester-acid imide foam plastics as claimed in claim 1, it is characterized in that raw materials used 3,3 ', 4,4 ', purity >=99.5% of-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 ', the mass ratio of-benzophenone tetracarboxylic dianhydride and polyether glycol is 10%～20%.
5. the preparation method of Green Flammability hard polyaminoester-acid imide foam plastics as claimed in claim 1, is characterized in that fire retardant used is: the particle diameter≤1.6 μ m of zinc borate, and the mass ratio of zinc borate and polyether glycol is 5%～10%; Kaolinic particle diameter≤2.6 μ m, the mass ratio of kaolin and polyether glycol is 2%～5%; Particle diameter≤10 μ the m of hollow glass microballoon, the mass ratio of hollow glass microballoon and polyether glycol is 2%～5%.
6. the preparation method of Green Flammability hard polyaminoester-acid imide foam plastics as claimed in claim 1, is characterized in that being adjuvant usedly: water, and the mass ratio of water and polyether glycol is 0.2%～0.5%; Skellysolve A, analytical pure, the mass ratio of Skellysolve A and polyether glycol is 0.8%～1.0%; Trolamine, analytical pure, the mass ratio of trolamine and polyether glycol is 0.04%～0.06%; Stannous octoate, analytical pure, the mass ratio of stannous octoate and polyether glycol is 0.06%～0.08%; Di-alcohol methyl ether, analytical pure, the mass ratio of di-alcohol methyl ether and polyether glycol is 0.3%～0.5%; Dimethyl silicone oil, analytical pure, the mass ratio of dimethyl silicone oil and polyether glycol is 0.2%～0.25%.
7. the preparation method of Green Flammability hard polyaminoester-acid imide foam plastics as claimed in claim 1, the preparation method who it is characterized in that inorganic composite flame retardants is: (1) takes 5～8 parts of dry nano-zinc borates and a certain amount of titanate coupling agent TM-48, join respectively in 50mL and 10ml Virahol, ultrasonic wave is disperseed 15～20min, magnetic agitation 15～20min.Mix above-mentioned two kinds of solution, ultrasonic wave is disperseed 20～25min, then in water bath with thermostatic control, react for some time, and suction filtration, vacuum-drying, grinding is sieved, and obtains the nano-zinc borate of surface modification; (2) take 2～3 parts of intercalator potassium acetates and 1～2 part of kaolin is placed on natural deliquescence 12h in mortar, grind 5h, with suction filtration after absolute ethanol washing three times, 80 ℃ of vacuum-drying 12h, then grind 200 mesh sieves, obtained the kaolin powder of potassium acetate intercalation modifying; (3) taking 2～3 parts of hollow glass microbeads is distributed in polyoxyethylene glycol raw material, then the polyoxyethylene glycol that respectively 10～15ml is contained to hollow glass microbead and 15～20ml isocyanic ester are dispersed in sodium dodecyl benzene sulfonate aqueous solution, mix above-mentioned two kinds of solution, ultrasonic wave is disperseed 10～15min, in electric stirring, carry out interfacial polymerization, through suction filtration, vacuum-drying, then ground 200 mesh sieves, obtaining polyurethane elastomer is cyst wall, and hollow glass microballoon is the microcapsule particle of the capsule heart; (4) take respectively 100 parts of kaolin after zinc borate, 20～50 parts of modifications after modification and the hollow glass microballoon after 20～50 parts of modifications and in star-like ball mill, carry out dry mixed, mixing time is 2～5h, obtains inorganic composite flame retardants.
8. the preparation method of Green Flammability hard polyaminoester-acid imide foam plastics as claimed in claim 1, the preparation method who it is characterized in that polyimide prepolymer is: (1) at room temperature prepares 3,3 ', 4,4 ', the N of-benzophenone tetracarboxylic dianhydride, N ',-dimethyl formamide saturated solution, polyisocyanates and saturated solution are stirred and reacted under oil bath heating, temperature of reaction is 60～80 ℃, and the reaction times is 20～30min, and rotating speed is 1500～2000r/min; (2) oil bath temperature is increased to 120～130 ℃, N
2protection, the reaction times is 10～15min, and rotating speed is 1000～1500r/min, and the standing 2～3h of cool to room temperature obtains polyimide prepolymer.
9. the preparation method of Green Flammability hard polyaminoester-acid imide foam plastics as claimed in claim 1, is characterized in that the foaming ageing method of hard polyaminoester-acid imide foam plastics is: (1) mixes with 100 parts of polyether glycols 0.2～0.25 part of 1～20 part of composite inorganic fire retardant, 0.2～0.25 part, water, 0.8～1.0 part of Skellysolve A, 0.04～0.06 part of trolamine, 0.06～0.08 part of stannous octoate, 0.3～0.5 part of di-alcohol methyl ether, dimethyl silicone oil according to its weight proportion; (2) will after this mixture and the stirring of polyimide prepolymer short mix, pour in preset mould and foam, wherein mold preheating temperature is 30～40 ℃, foamed time is 5～10min, finally foam materials is put into and in vacuum drying oven, carries out slaking, 90～100 ℃ of curing temperatures, curing time 12h, obtains hard polyaminoester-acid imide foam plastics with Green Flammability characteristic.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086995A (en) * | 2014-07-14 | 2014-10-08 | 南京航空航天大学 | Hollow microspheres-enhanced polyimide matrix foamed composite material and preparation method thereof |
| CN105852449A (en) * | 2016-05-26 | 2016-08-17 | 程南南 | Wall-mounted cabinet with fire-extinguishing device and fire protection coating |
| CN109642007A (en) * | 2016-08-26 | 2019-04-16 | 巴斯夫欧洲公司 | The method for preparing the foam of polymers containing imide group |
| CN109824860A (en) * | 2019-03-07 | 2019-05-31 | 中国科学院长春应用化学研究所 | A kind of polyurethane polyureas acid imide foam material and preparation method thereof |
| CN115181422A (en) * | 2021-04-02 | 2022-10-14 | 中国科学院大连化学物理研究所 | Polyimide foam material based flame retardant and preparation method and application thereof |
| EP4386027A1 (en) | 2022-12-12 | 2024-06-19 | Basf Se | Solvent-free process to produce imide-containing isocyanate prepolymers |
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2013
- 2013-12-06 CN CN201310694612.0A patent/CN103755956A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086995A (en) * | 2014-07-14 | 2014-10-08 | 南京航空航天大学 | Hollow microspheres-enhanced polyimide matrix foamed composite material and preparation method thereof |
| CN105852449A (en) * | 2016-05-26 | 2016-08-17 | 程南南 | Wall-mounted cabinet with fire-extinguishing device and fire protection coating |
| CN109642007A (en) * | 2016-08-26 | 2019-04-16 | 巴斯夫欧洲公司 | The method for preparing the foam of polymers containing imide group |
| CN109824860A (en) * | 2019-03-07 | 2019-05-31 | 中国科学院长春应用化学研究所 | A kind of polyurethane polyureas acid imide foam material and preparation method thereof |
| CN115181422A (en) * | 2021-04-02 | 2022-10-14 | 中国科学院大连化学物理研究所 | Polyimide foam material based flame retardant and preparation method and application thereof |
| CN115181422B (en) * | 2021-04-02 | 2023-06-27 | 中国科学院大连化学物理研究所 | Flame retardant based on polyimide foam material and preparation method and application thereof |
| EP4386027A1 (en) | 2022-12-12 | 2024-06-19 | Basf Se | Solvent-free process to produce imide-containing isocyanate prepolymers |
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Application publication date: 20140430 |