CN101544720A - Flame-resisting MAA/AN copolymer foam plastic and preparation method of flame-resisting agent used by the same - Google Patents
Flame-resisting MAA/AN copolymer foam plastic and preparation method of flame-resisting agent used by the same Download PDFInfo
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- CN101544720A CN101544720A CN200910022402A CN200910022402A CN101544720A CN 101544720 A CN101544720 A CN 101544720A CN 200910022402 A CN200910022402 A CN 200910022402A CN 200910022402 A CN200910022402 A CN 200910022402A CN 101544720 A CN101544720 A CN 101544720A
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Abstract
The preparation formula of flame-resisting MAA/AN copolymer foam plastic consists of a monomer 1 (methacrylic acid MAA), a monomer 2 (acrylonitrile AN), an initiator, a cross-linker, a foaming agent, a nucleating agent, a molecular weight regulator and a flame-resisting agent (3-chloro-2-hydroxypropyl dimethyl phosphate or ammonium (3-chloro-2-hydroxyl) propyl phosphate). The preparation procedure is as follows: polymerizing the formula mixed solution into a foamable copolymer plate in a closed die, foaming and post-processing the foamable copolymer plate into a structurally flame-resisting MAA/AN copolymer foam plastic at a high temperature. The flame-resisting agent 3-chloro-2-hydroxypropyl dimethyl phosphate is synthesized by dimethyl phosphate, epoxy chloropropane and sodium alcoholate, and the other flame-resisting agent ammonium (3-chloro-2-hydroxyl) propyl phosphate is synthesized by phosphoric acid, epoxy chloropropane and carbomite or ammonium carbonate or ammonium bicarbonate, respectively. The invention achieves the structural flame resistance of MAA/AN copolymer foam plastic.
Description
Technical field
The present invention relates to a kind of MAA/AN copolymer foam plastic, concrete is fire-retardant MAA/AN copolymer foam plastic; The preparation method who also relates to the used fire retardant of this fire-retardant MAA/AN copolymer foam plastic.
Background technology
Document 1 " patent No. is the Chinese patent of ZL200610091394.1 " discloses a kind of MAA/AN copolymer foam plastic and preparation method thereof, and the recipe ingredient of this MAA/AN copolymer foam plastic presses row weight part ratio polyreaction and foaming forms: monomer 1: methacrylic acid 42～62
Monomer 2: vinyl cyanide 58～38
Initiator: Diisopropyl azodicarboxylate 0.18～0.40
Linking agent: acrylamide or Methacrylamide 1.3～3.5
Whipping agent: methane amide or propylene glycol or amylalcohol or hexanol 2.0～8.0
Nucleator: urea 0.3～1.3.
Document 2 " enhancing of AN/MAA copolymer foam plastic and fire-retardant research Northwestern Polytechnical University's master thesis in April, 2008, Dong Shanlai " discloses a kind of enhancing and fire-retardant research of AN/MAA copolymer foam plastic.Research thinks that the matrix resin of AN/MAA copolymer foam plastic is not fire-retardant, and the porous plastics specific surface area is big, and this AN/MAA copolymer foam plastic burns easily, and its combustion limits oxygen index (LOI value) is 21～23%, and vertical combustion is strong and quick.
Document 3 " patent No. is 4576971 United States Patent (USP) " discloses a kind of method of the PMI of realization porous plastics, and this patent is a fire retardant by add methyl-phosphoric acid dimethyl ester (DMMP) in the prescription of preparation PMI porous plastics.But DMMP is an additive flame retardant, and the matrix resin of PMI porous plastics is had very strong plastification, and the mechanical property of PMI porous plastics, resistance toheat are descended significantly.
Summary of the invention
In order to overcome the deficiency of existing MAA/AN copolymer foam plastic flame retardant properties difference, the invention provides a kind of fire-retardant MAA/AN copolymer foam plastic, adopt liquid flame retardant, can improve its combustion limits oxygen index.
The present invention also provides the preparation method of liquid flame retardant.
The technical solution adopted for the present invention to solve the technical problems: a kind of fire-retardant MAA/AN copolymer foam plastic, its recipe ingredient press row weight part ratio polyreaction and foaming forms:
Monomer 1: methacrylic acid MAA 42～62
Monomer 2: vinyl cyanide AN 58～38
Initiator: Diisopropyl azodicarboxylate 0.18～0.40
Linking agent: acrylamide or Methacrylamide 1.3～3.5
Whipping agent: methane amide or propylene glycol or amylalcohol or hexanol 2.0～8.0
Nucleator: urea 0.3～1.3
Fire retardant 5～15;
Described fire retardant be 3-chloro-2-hydroxypropyl dimethyl phosphate (DMCPP) or 3-chloro-2-hydroxy propyl ester di-ammonium salts (CPAP) any.
The preparation method of a kind of above-mentioned fire retardant DMCPP is characterized in comprising the steps:
(a) with dimethylphosphite and sodium methylate according to mol ratio 1.0～1.2:1, under 40～60 ℃ of conditions, react, generate dimethylphosphite sodium;
(b) drip epoxy chloropropane in dimethylphosphite sodium, mol ratio is 1:1, and reacts 1h under 40～60 ℃ of conditions, generates phosphate epoxypropyl dimethyl ester and precipitated sodium chloride (NaCl);
(c) with the phosphate epoxypropyl dimethyl ester 40～60 ℃ of temperature, under 3～6kPa pressure condition, steam methyl alcohol and excessive dimethylphosphite obtains low-viscosity (mobile) liquid;
(d) step (c) product is added drop-wise in the normal temperature hydrogen chloride methanol solution to neutral;
(e) steam methyl alcohol and suction filtration is removed NaCl, obtain DMCPP.
The preparation method of a kind of above-mentioned fire retardant CPAP is characterized in comprising the steps:
(f) be slowly to drip epoxy chloropropane in the phosphate aqueous solution of 20-30% to concentration, phosphoric acid and epoxy chloropropane mol ratio are 1:1, drip afterwards to react 2～4h under 40～60 ℃ of conditions, obtain the oyster white thick liquid;
(g) be that the carboxamide of 20-30% or ammonium carbonate solution or ammonium bicarbonate aqueous solution are added drop-wise in step (f) reaction product with the concentration of configuration, the mol ratio of carboxamide or volatile salt and initial feed phosphoric acid is 1:1, the mol ratio of bicarbonate of ammonia and initial feed phosphoric acid is 2:1, react 2～4h under 80～90 ℃ of conditions then, obtain the water white transparency thick liquid;
(h) vacuum-drying obtains thickness product C PAP under 100～120 ℃ of conditions.
The invention has the beneficial effects as follows: owing in MAA/AN copolymer foam plastic prescription, added fire retardant DMCPP or CPAP, prepared fire-retardant MAA/AN copolymer foam plastic combustion limits oxygen index (LOI value) brings up to 28%～32% by 21～23% of prior art, and behind fire, extinguish fast, do not have dropping in the burning.
Two kinds of fire retardants of the inventive method preparation are the structure-type fire retardants with active functionality, can excellent dissolution in the raw material mixed solution of preparation MAA/AN copolymer foam plastic, fire retardant contains phosphorus-halogen element, can react with the molecular chain of MAA/AN copolymer foam plastic and be connected on the molecular chain, realize that the structure-type of high-performance MAA/AN copolymer foam plastic is fire-retardant.
Below in conjunction with drawings and Examples the present invention is elaborated.
Description of drawings
Fig. 1 is the influence curve of the prepared fire retardant DMCPP consumption of the inventive method to MAA/AN copolymer foam plastic LOI value.
Fig. 2 is the influence curve of the prepared fire retardant CPAP consumption of the inventive method to MAA/AN copolymer foam plastic LOI value.
Embodiment
Fire-retardant MAA/AN copolymer foam plastic, its preparation prescription is made up of monomer 1, monomer 2, initiator, linking agent, whipping agent, nucleator and synthetic fire retardant, and its recipe ingredient is by weight than counting:
Monomer 1: methacrylic acid 42～62
Monomer 2: vinyl cyanide 58～38
Initiator: Diisopropyl azodicarboxylate 0.18～0.40
Linking agent: acrylamide or Methacrylamide 1.3～3.5
Whipping agent: methane amide or propylene glycol or amylalcohol or hexanol 2.0～8.0
Nucleator: urea 0.3～1.3
Fire retardant: DMCPP or CPAP 5～15;
The preparation method of above-mentioned fire-retardant MAA/AN copolymer foam plastic comprises the steps:
Step 1, above-mentioned prescription is mixed, form even stock liquid;
Step 2, stock liquid is poured in the mould of being made by two dull and stereotyped unorganic glasses and natural rubber or terpolymer EP rubber or silicone rubber O-ring, the glass mold outside is stepped up by anchor clamps;
Step 3, have the glass mold of stock liquid to put into strong circulator bath device filling to carry out polymerization, form transparent foamed MAA/AN copolymerization sheet, polymerizing condition: 40～60 ℃ of water temperatures, time 24～72h.
Step 4, the foamed MAA/AN copolymerization sheet (as baking oven, drying tunnel etc.) in 180～200 ℃ strong recirculated hot air that step 3 is obtained carry out free foaming and become porous plastics.
The used structure-type fire retardant of the present invention DMCPP structural formula is shown in structural formula I.The synthesis step of DMCPP is as follows, and composition principle is shown in reaction formula 1～3:
Step 1, with dimethylphosphite and sodium methylate according to mol ratio 1.0～1.2:1, under 40～60 ℃ of conditions, react, generate dimethylphosphite sodium;
Step 2, in dimethylphosphite sodium, drip the epoxy chloropropane with dimethylphosphite sodium equimolar amount, and under 40～60 ℃ of conditions, react 1h, generate the phosphate epoxypropyl dimethyl ester and also separate out NaCl;
Step 3, with the phosphate epoxypropyl dimethyl ester 40～60 ℃ of temperature, under 3～6kPa pressure condition, steam methyl alcohol and excessive dimethylphosphite obtains low-viscosity (mobile) liquid;
Step 4, the step 3 product is added drop-wise in the normal temperature hydrogen chloride methanol solution to neutral;
Structural formula (I) DMCPP
The structural formula of the used structure-type fire retardant of the present invention CPAP is shown in structural formula II.The synthesis step of CPAP is as follows, and composition principle is shown in reaction formula 4,5:
Step 1, in the phosphoric acid of demarcating concentration, slowly drip the equimolar amount epoxy chloropropane, drip under 40～60 ℃ of conditions in back and react 2～4h, obtain the oyster white thick liquid;
Step 2, the ammonium bicarbonate aqueous solution with the carboxamide phosphoric acid equimolar amount or ammonium carbonate solution or twice molar weight that will dispose are added drop-wise in the step 1 reaction product, react 2～4h under 80～90 ℃ of conditions, obtain the water white transparency thick liquid;
Step 3, vacuum-drying obtains thickness product C PAP under 100～120 ℃ of conditions.
Structure-type fire retardant DMCPP that the present invention is prepared and CPAP are under foaming and heat treated high temperature, molecular chain generation esterification with the MAA/AN copolymer foam plastic, shown in reaction formula 6,7, thereby the structure-type of realizing the MAA/AN copolymer foam plastic is fire-retardant.
It is that the prepared MAA/AN copolymer foam plastic of fire retardant has excellent flame-retardant performance that the present invention adopts DMCPP or CPAP, the fire retardant consumption is 10～20% o'clock, prepared MAA/AN copolymer foam plastic LOI value can reach 28%～32%, and behind fire, extinguish fast, do not have dropping in the burning.
Table 1 is depicted as embodiment 1, the embodiment 2 of the fire-retardant MAA/AN copolymer foam plastic of preparation, the preparation prescription of embodiment 3, embodiment 4.
The embodiment of the MAA/AN copolymer foam plastic of table 1 preparation.
According to embodiment 1, embodiment 2, embodiment 3, embodiment 4 preparation raw material liquid; Stock liquid is poured in the mould of being made by two dull and stereotyped unorganic glasses and rubber seal, put into 54 ℃ of water-bath polymerase 17s of strong circulation 2h MAA/AN copolymerization sheet that obtains to foam.The foamed MAA/AN copolymerization sheet that embodiment 1,2,3 and reference examples obtain free foaming in 180 ℃ of baking ovens is the MAA/AN copolymer foam plastic, and the foamed MAA/AN copolymerization sheet that embodiment 4 obtains free foaming in 200 ℃ of baking ovens is the MAA/AN copolymer foam plastic.The porous plastics that embodiment and reference examples obtain all in 140 ℃ of baking ovens thermal treatment 4h then at 160 ℃ of baking oven thermal treatment 4h.
It is 60kg/m that embodiment 1 obtains density
3Deflagration MAA/AN copolymer foam plastic, it is 60kg/m that embodiment 2 obtains density
3Fire-retardant MAA/AN copolymer foam plastic, it is 80kg/m that embodiment 3 obtains density
3Flame-retarded foamed plastic, it is 110kg/m that embodiment 4 obtains density
3Flame-retarded foamed plastic.Reference examples obtains that density is 60,80kg/m
3Non-fire-retardant MAA/AN copolymer foam plastic.
The combustionproperty of the fire-retardant MAA/AN porous plastics of embodiment 1～4 resulting structure-type is as shown in table 2, with document 1 contrast.
The combustionproperty of the fire-retardant MAA/AN copolymer foam plastic of table 2 structure-type
Claims (3)
1, a kind of fire-retardant MAA/AN copolymer foam plastic, its recipe ingredient press row weight part ratio polyreaction and foaming forms: monomer 1: methacrylic acid 42～62
Monomer 2: vinyl cyanide 58～38
Initiator: Diisopropyl azodicarboxylate 0.18～0.40
Linking agent: acrylamide or Methacrylamide 1.3～3.5
Whipping agent: methane amide or propylene glycol or amylalcohol or hexanol 2.0～8.0
Nucleator: urea 0.3～1.3,
It is characterized in that also comprising the fire retardant of 5～15 weight parts, described fire retardant be 3-chloro-2-hydroxypropyl dimethyl phosphate or phosphoric acid (3-chloro-2-hydroxyl) propyl ester di-ammonium salts any.
2, the preparation method of the described fire retardant 3-of a kind of claim 1 chloro-2-hydroxypropyl dimethyl phosphate is characterized in comprising the steps:
(a) with dimethylphosphite and sodium methylate according to mol ratio 1.0～1.2:1, under 40～60 ℃ of conditions, react, generate dimethylphosphite sodium;
(b) drip epoxy chloropropane in dimethylphosphite sodium, mol ratio is 1:1 and reacts 1h under 40～60 ℃ of condition, generates phosphate epoxypropyl dimethyl ester and precipitated sodium chloride;
(c) with the phosphate epoxypropyl dimethyl ester 40～60 ℃ of temperature, under 3～6kPa pressure condition, steam methyl alcohol and excessive dimethylphosphite obtains low-viscosity (mobile) liquid;
(d) step (c) product is added drop-wise in the normal temperature hydrogen chloride methanol solution to neutral;
(e) steam methyl alcohol and suction filtration is removed NaCl, obtain 3-chloro-2-hydroxypropyl dimethyl phosphate.
3, the preparation method of the described fire retardant phosphoric acid of a kind of claim 1 (3-chloro-2-hydroxyl) propyl ester di-ammonium salts is characterized in comprising the steps:
(f) be slowly to drip the equimolar amount epoxy chloropropane in the phosphate aqueous solution of 20-30% to concentration, drip under 40～60 ℃ of conditions in back and react 2～4h, obtain the oyster white thick liquid;
(g) will with the carboxamide of phosphoric acid equimolar amount or the ammonium bicarbonate aqueous solution of ammonium carbonate solution or twice molar weight, be added drop-wise to then in step (f) reaction product, react 2～4h under 80～90 ℃ of conditions, obtain the water white transparency thick liquid;
(h) vacuum-drying obtains thickness product phosphoric acid (3-chloro-2-hydroxyl) propyl ester di-ammonium salts under 100～120 ℃ of conditions.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011138060A1 (en) | 2010-05-06 | 2011-11-10 | Evonik Röhm Gmbh | Polymethacrylimide foam materials having reduced flammability and method for producing same |
| CN103539890A (en) * | 2013-10-23 | 2014-01-29 | 江苏兆鋆新材料科技有限公司 | Preparation method of halogen-free flame retardant AN/MAA (acrylic nitrile/methyl acrylic acid) copolymer foam material |
| CN103641961A (en) * | 2013-11-29 | 2014-03-19 | 浙江天和树脂有限公司 | Low-cost halogen-free chemical flame-retardant vinyl ester resin and preparation method thereof |
| CN104086695A (en) * | 2014-06-23 | 2014-10-08 | 浙江中科恒泰新材料科技有限公司 | Flame-retardant poly(methyl)acrylimide foamed plastic with high strength and heat resistance |
| CN104945553A (en) * | 2015-07-21 | 2015-09-30 | 江苏兆鋆新材料股份有限公司 | Preparation method and application of high-tenacity foam material |
| CN105669893A (en) * | 2016-04-14 | 2016-06-15 | 无锡智谷锐拓技术服务有限公司 | Flame-retardant foamed plastic |
| CN106565888A (en) * | 2016-10-14 | 2017-04-19 | 浙江中科恒泰新材料科技有限公司 | Preparation method of flame retardant polymethacrylimide foam and product thereof |
| CN106939511A (en) * | 2017-04-21 | 2017-07-11 | 齐齐哈尔大学 | A kind of phosphorus nitrogen chlorine-resistant fire retardant and its synthetic method |
| CN109281173A (en) * | 2018-08-09 | 2019-01-29 | 道晟拉链科技（太仓）有限公司 | A kind of high-performance refractory agent and preparation method thereof for zipper |
| CN109810222A (en) * | 2017-11-22 | 2019-05-28 | 财团法人工业技术研究院 | The preparation method of carbon fiber precursor composition and carbon fiber predecessor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3346060A1 (en) * | 1983-12-21 | 1985-07-04 | Röhm GmbH, 6100 Darmstadt | FLAME-RETARDED POLYACRYLIC OR POLYMETHACRYLIMIDE FOAM AND METHOD FOR THE PRODUCTION THEREOF |
| US7507399B1 (en) * | 2004-08-05 | 2009-03-24 | Surfatech Corporation | Functionalized polymeric surfactants based upon alkyl polyglycosides |
| CN100420702C (en) * | 2005-07-28 | 2008-09-24 | 西北工业大学 | MAA/AN copolymer foamed plastic and its preparation method |
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2009
- 2009-05-07 CN CN2009100224020A patent/CN101544720B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102010028695A1 (en) | 2010-05-06 | 2011-11-10 | Evonik Röhm Gmbh | Polymethacrylimide foams with reduced flammability and process for the preparation of these |
| WO2011138060A1 (en) | 2010-05-06 | 2011-11-10 | Evonik Röhm Gmbh | Polymethacrylimide foam materials having reduced flammability and method for producing same |
| CN103539890A (en) * | 2013-10-23 | 2014-01-29 | 江苏兆鋆新材料科技有限公司 | Preparation method of halogen-free flame retardant AN/MAA (acrylic nitrile/methyl acrylic acid) copolymer foam material |
| CN103641961B (en) * | 2013-11-29 | 2017-01-11 | 浙江天和树脂有限公司 | Low-cost halogen-free chemical flame-retardant vinyl ester resin and preparation method thereof |
| CN103641961A (en) * | 2013-11-29 | 2014-03-19 | 浙江天和树脂有限公司 | Low-cost halogen-free chemical flame-retardant vinyl ester resin and preparation method thereof |
| CN104086695A (en) * | 2014-06-23 | 2014-10-08 | 浙江中科恒泰新材料科技有限公司 | Flame-retardant poly(methyl)acrylimide foamed plastic with high strength and heat resistance |
| CN104945553A (en) * | 2015-07-21 | 2015-09-30 | 江苏兆鋆新材料股份有限公司 | Preparation method and application of high-tenacity foam material |
| CN104945553B (en) * | 2015-07-21 | 2016-09-14 | 江苏兆鋆新材料股份有限公司 | A kind of preparation method and applications of high tenacity foamed materials |
| CN105669893A (en) * | 2016-04-14 | 2016-06-15 | 无锡智谷锐拓技术服务有限公司 | Flame-retardant foamed plastic |
| CN106565888A (en) * | 2016-10-14 | 2017-04-19 | 浙江中科恒泰新材料科技有限公司 | Preparation method of flame retardant polymethacrylimide foam and product thereof |
| CN106939511A (en) * | 2017-04-21 | 2017-07-11 | 齐齐哈尔大学 | A kind of phosphorus nitrogen chlorine-resistant fire retardant and its synthetic method |
| CN109810222A (en) * | 2017-11-22 | 2019-05-28 | 财团法人工业技术研究院 | The preparation method of carbon fiber precursor composition and carbon fiber predecessor |
| CN109810222B (en) * | 2017-11-22 | 2021-03-30 | 财团法人工业技术研究院 | Carbon fiber precursor composition and preparation method of carbon fiber precursor |
| CN109281173A (en) * | 2018-08-09 | 2019-01-29 | 道晟拉链科技（太仓）有限公司 | A kind of high-performance refractory agent and preparation method thereof for zipper |
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