CN101475683B - Process for producing flame-retardant hyperbranched polymer - Google Patents
Process for producing flame-retardant hyperbranched polymer Download PDFInfo
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- CN101475683B CN101475683B CN2009100290234A CN200910029023A CN101475683B CN 101475683 B CN101475683 B CN 101475683B CN 2009100290234 A CN2009100290234 A CN 2009100290234A CN 200910029023 A CN200910029023 A CN 200910029023A CN 101475683 B CN101475683 B CN 101475683B
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Abstract
The invention relates to a preparation method for a fire retardation type hyperbranched polymer. The preparation method comprises the following steps: taking polyol or polybasic amine or the mixture of polyol and polybasic amine as a first monomer, taking a phosphatic bichloride or phosphorus oxychloride as a second monomer, taking polyatomic acid or anhydride as a third monomer, and carrying out the reaction of the three monomers in the presence of a catalyst and an organic solvent at a temperature of between 40 and 200 DEG C for 4 to 20 hours to prepare the fire retardation type hyperbranched polymer. The mol ratio of the first monomer to the second monomer to the third monomer is 1:0.05 to 1.0:0.25 to 2; and the dosage of the catalyst is 0.1 to 2 percent of the total mass of the three monomers. The method uses polyatomic acid or anhydride thereof to replace phosphorus oxychloride or dichlor phosphide with higher prices, thereby bringing about lower raw material cost and a simple preparation process route. In addition, the prepared hyperbranched polymer contains phosphate ester groups with the function of fire retardation and has good compatibility with other high molecular materials. Therefore, the hyperbranched polymer can be used as a reinforcing and plasticizing fire retardant in the fields of plastics, coatings, adhesives and the like.
Description
Technical field
The present invention relates to a kind of preparation method of flame-retardant hyperbranched polymer.
Background technology
Kim etc. utilizes AB from the nineties in 20th century
XSince the synthetic hyperbranched poly benzene of polycondensation between the type monomer molecule, hyperbranched polymer is because the relatively easy and special people's keen interest that causes of performance of preparation.It is that single stage method can make that hyperbranched polymer adopts the monomer mass polymerization, do not need purify careful the separation, hyperbranched polymer have good hydrodynamic performance, unique viscosity behavior, easily film forming, be difficult for crystallization, good solubility, machinable three-dimensional structure and advantage such as self-crosslinking do not take place, be expected to be able to widespread use in fields such as nanometer, self-assembly, liquid crystal, catalyzer, nonlinear optics, energy transformation and acceptance, medical carrier, functional agents.At present, existing lot of documents report is applied to the material flame retardant area with hyperbranched polymer.
Publication number is the preparation method that a kind of nitrogenous hyper branched polyphosphate ester has been put down in writing in the Chinese invention patent application of CN101182375, this method is with (A) nitrogenous trihydroxy-compound or dihydroxyl amine compound or triamino compound, (B) phosphorous dichloro compound or phosphorus oxychloride, (C) 0.1～2% catalyzer of monomer weight, four kinds of materials of organic solvent are added to prolong are housed, in the reactor of thermometer and whipping appts, logical nitrogen, 40～200 ℃ of reactions 4～20 hours, when no hydrogen chloride gas is emitted, filter solids, filtrate is vacuumized organic solvent at 100～120 ℃.The nitrogenous hyper branched polyphosphate ester of this method gained can be applicable to the halogen-free flame retardants field, but owing to need to consume a large amount of phosphorus oxychloride or dichloro phosphide in this method, causes production cost higher.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of preparation method of flame-retardant hyperbranched polymer is provided, and production cost is low.
For solving above technical problem, the following technical scheme that the present invention takes:
A kind of preparation method of flame-retardant hyperbranched polymer, with polyvalent alcohol or polyamine or their mixture is first monomer, with phosphorous dichloro compound or phosphorus oxychloride is second monomer, with polyprotonic acid or acid anhydrides is the 3rd monomer, three kinds of described monomers are in the presence of catalyzer and organic solvent, made described flame-retardant hyperbranched polymer in 4～20 hours in 40～200 ℃ of reactions, first monomer, second monomer and the 3rd monomeric mol ratio are 1: 0.05～1.0: 0.25～2, and described catalyst levels is 0.1～2% of three kinds of monomer total masses.
Described polyvalent alcohol is preferably one or more in the following compounds:
HO (CH
2)
N+2OH, HO (CH
2CH
2)
N+1OCH
2CH
2OH, glycerine and TriMethylolPropane(TMP), wherein m, n, k are 0～8 integer.
In the preferred following compounds of described polyamine one or more:
HN
2(CH
2)
A+2NH
2, 4,4 '-diaminodiphenylmethane and 4,4 '-diamino hexichol, wherein a, b, i are 0～8 integer.
Described phosphorous dichloro compound is preferably C
6H
5POCl
2Or CH
3(CH
2)
fPOCl
2, wherein, f is 0～8 integer.
One or more of the preferred tetrabutyl titanate of described catalyzer, zinc acetate, sulfuric acid, phosphoric acid, metatitanic acid orthocarbonate, tosic acid, methylsulfonic acid.
Described organic solvent is preferably one or more the mixed solvent in toluene, dimethylbenzene, dimethyl formamide, the N,N-DIMETHYLACETAMIDE.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
The present invention replaces higher phosphorus oxychloride or the dichloro phosphide of part price with polyprotonic acid or its acid anhydrides, reduces raw materials cost.Simultaneously, contain the bound phosphate groups that can play fire retardation in the hyperbranched polymer that adopts present method to make, itself and other macromolecular material has good consistency, therefore can be used as the toughness reinforcing and flame retardant of enhancing in fields such as plastics, coating, tackiness agent.
Embodiment
The present invention will be described in detail below in conjunction with specific embodiment, but be not limited to these embodiment.
Embodiment 1
0.3mol diethanolamine, 0.05mol phosphorus oxychloride, 0.05mol trimellitic acid 1,2-anhydride, 100ml dimethylbenzene, 10mlDMF and 0.24g tosic acid are added in the four-hole boiling flask that condensing works, water trap, agitator, thermometer are housed, under the agitation condition, logical nitrogen, slowly be warmed up under 140～160 ℃ of conditions and reacted about about 8 hours, vacuumize organic solvent at 100～120 ℃ then, obtain the terminal hydroxy group flame-retardant hyperbranched polymer.
Embodiment 2
With 0.2mol phthalic anhydride, 0.28mol TriMethylolPropane(TMP), 0.1mol CH
3POCl
2, 120ml toluene and 0.40g tosic acid be added in the four-hole boiling flask that condensing works, water trap, agitator, thermometer are housed, under the agitation condition, logical nitrogen, slowly be warmed up under 130～150 ℃ of conditions and reacted about about 10 hours, vacuumize organic solvent at 100～120 ℃ then, obtain the terminal hydroxy group flame-retardant hyperbranched polymer.
Embodiment 3
With 0.10mol phthalic acid, 0.28mol trolamine, 0.20mol C
6H
5POCl
2, 150ml dimethylbenzene and 0.69g sulfuric acid is added in the four-hole boiling flask that condensing works, water trap, agitator, thermometer are housed, under the agitation condition, logical nitrogen, slowly be warmed up under 150～160 ℃ of conditions and reacted about about 7 hours, vacuumize organic solvent at 100～120 ℃ then, obtain the terminal hydroxy group flame-retardant hyperbranched polymer.
Embodiment 4
0.15mol phthalic acid, 0.28mol phthalic anhydride, 0.28mol trihydroxyethyl cyanurate, 0.15molC6H5POCl2,150ml dimethylbenzene, 20mlDMAc and 1.56g phosphoric acid are added in the four-hole boiling flask that condensing works, water trap, agitator, thermometer are housed, under the agitation condition, logical nitrogen, slowly be warmed up under 160～170 ℃ of conditions and reacted about about 8 hours, vacuumize organic solvent at 100～120 ℃ then, obtain holding the carboxyl flame-retardant hyperbranched polymer.
Embodiment 5
0.15mol hexanodioic acid, 0.06mol phthalic acid, 0.10mol glycerine, 0.20mol TriMethylolPropane(TMP), 0.10mol C6H5POCl2,150ml dimethylbenzene and 0.65g tetrabutyl titanate are added in the four-hole boiling flask that condensing works, water trap, agitator, thermometer are housed, under the agitation condition, logical nitrogen, slowly be warmed up under 170～180 ℃ of conditions and reacted about about 6 hours, vacuumize organic solvent at 100～120 ℃ then, obtain the terminal hydroxy group flame-retardant hyperbranched polymer.
Embodiment 6
0.15mol trimellitic acid 1,2-anhydride, 0.47mol hexanodioic acid, 0.21mol glycol ether, 0.01mol phosphorus oxychloride, 150ml dimethylbenzene and 0.61g sulfuric acid are added in the four-hole boiling flask that condensing works, water trap, agitator, thermometer are housed, under the agitation condition, logical nitrogen, slowly be warmed up under 160～170 ℃ of conditions and reacted about about 7 hours, vacuumize organic solvent at 100～120 ℃ then, obtain holding the carboxyl flame-retardant hyperbranched polymer.
Embodiment 7
With 0.15mol 1,3,5-three carboxyl benzene, 0.11mol butyleneglycol, 0.10mol propylene glycol, 0.03mol phosphorus oxychloride, 0.04mol C2H5POCl2,150ml dimethylbenzene and 0.43g zinc acetate are added in the four-hole boiling flask that condensing works, water trap, agitator, thermometer are housed, under the agitation condition, logical nitrogen, slowly be warmed up under 160～170 ℃ of conditions and reacted about about 8 hours, vacuumize organic solvent at 100～120 ℃ then, obtain holding the carboxyl flame-retardant hyperbranched polymer.
Embodiment 8
0.15mol trimellitic acid 1,2-anhydride, 0.36mol quadrol, 0.05mol phosphorus oxychloride, 120ml dimethylbenzene, 30mlDMF and 0.35g phosphoric acid are added in the four-hole boiling flask that condensing works, water trap, agitator, thermometer are housed, under the agitation condition, logical nitrogen, slowly be warmed up under 100～110 ℃ of conditions and reacted about about 16 hours, vacuumize organic solvent at 100～120 ℃ then, obtain holding amino flame-retardant hyperbranched polymer.
Embodiment 9
With 0.15mol trimellitic acid 1,2-anhydride, 0.10mol phenylenediamine, 0.08mol propylene diamine, 0.05molC2H5POCl2,120ml dimethylbenzene and 0.32g added methanesulfonic acid in the four-hole boiling flask that condensing works, water trap, agitator, thermometer are housed, under the agitation condition, logical nitrogen, slowly be warmed up under 130～140 ℃ of conditions and reacted about about 12 hours, vacuumize organic solvent at 100～120 ℃ then, obtain holding the carboxyl flame-retardant hyperbranched polymer.
Embodiment 10
With 0.10mol hexanodioic acid, 0.11mol phthalic acid, 0.30mol 1,3,5-triaminobenzene, 0.10molC6H5POCl2,100ml dimethylbenzene and 0.67g metatitanic acid orthocarbonate are added in the four-hole boiling flask that condensing works, water trap, agitator, thermometer are housed, under the agitation condition, logical nitrogen, slowly be warmed up under 120～130 ℃ of conditions and reacted about about 14 hours, vacuumize organic solvent at 100～120 ℃ then, obtain holding the amido flame-retardant hyperbranched polymer.
The degree of branching of the hyperbranched polymer of embodiment 1～10 preparation adopts
1H-NMR (Macromolecules 1997,30,7024) technology is measured; The molecular weight of this hyperbranched polymer and molecular weight distributing index adopt the GPC technical testing, and are standard specimen with the polystyrene; Flame retardant properties is pressed GB/T2406-1993 test oxygen index, and is standard specimen with the virgin pp, in weight ratio, by 15 parts of hyperbranched polymers and 85 parts of polypropylene sample preparations.The performance of embodiment 1～10 prepared hyperbranched polymer sees Table 1.
The character of table 1 embodiment 1～10 prepared flame-retardant hyperbranched polymer
| Embodiment | Molecular weight, g/mol | Molecular weight distributing index | The degree of branching | Oxygen index, % |
| Standard specimen | - | - | - | 17.5 |
| Embodiment 1 | 2850 | 1.65 | 0.65 | 22.8 |
| Embodiment 2 | 4860 | 1.86 | 0.54 | 23.4 |
| Embodiment 3 | 5670 | 2.05 | 0.58 | 24.5 |
| Embodiment 4 | 12650 | 2.57 | 0.49 | 24.8 |
| Embodiment 5 | 6430 | 1.90 | 0.50 | 23.8 |
| Embodiment 6 | 14580 | 2.48 | 0.47 | 22.9 |
| Embodiment 7 | 15620 | 2.87 | 0.46 | 25.3 |
| Embodiment 8 | 7430 | 2.08 | 0.56 | 24.8 |
| Embodiment 9 | 21460 | 2.94 | 0.42 | 25.1 |
| Embodiment 10 | 18600 | 2.55 | 0.45 | 25.4 |
As seen from Table 1, good according to the hyperbranched polymer flame retardant properties of preparation method's preparation of the present invention, be suitable for the halogen-free flame retardants field.Compared with prior art, raw materials cost is lower, thereby reduces the production cost of hyperbranched polymer, is more suitable for suitability for industrialized production.
Claims (6)
1. the preparation method of a flame-retardant hyperbranched polymer, it is characterized in that: with polyvalent alcohol or polyamine or their mixture is first monomer, with phosphorous dichloro compound or phosphorus oxychloride is second monomer, with polyprotonic acid or acid anhydrides is the 3rd monomer, three kinds of described monomers are in the presence of catalyzer and organic solvent, made described flame-retardant hyperbranched polymer in 4～20 hours in 40～200 ℃ of reactions, first monomer, second monomer and the 3rd monomeric mol ratio are 1: 0.05～1.0: 0.25～2, and described catalyst levels is 0.1～2% of three kinds of monomer total masses.
2. the preparation method of a kind of flame-retardant hyperbranched polymer according to claim 1, it is characterized in that: described polyvalent alcohol is selected from one or more in the following compounds:
HO (CH
2)
N+2OH, HO (CH
2CH
2)
N+1OCH
2CH
2OH, glycerine and TriMethylolPropane(TMP), wherein m, n, k are greater than 0 and smaller or equal to 8 integer.
3. the preparation method of a kind of flame-retardant hyperbranched polymer according to claim 1, it is characterized in that: described polyamine is selected from one or more in the following compounds:
HN
2(CH
2)
A+2NH
2, 4,4 '-diaminodiphenylmethane and 4,4 '-diamino hexichol, wherein a, b, i are greater than 0 and smaller or equal to 8 integer.
4. the preparation method of a kind of flame-retardant hyperbranched polymer according to claim 1, it is characterized in that: described phosphorous dichloro compound is C
6H
5POCl
2Or CH
3(CH
2)
fPOCl
2, wherein, f is 0～8 integer.
5. the preparation method of a kind of flame-retardant hyperbranched polymer according to claim 1 is characterized in that: described catalyzer is selected from one or more of tetrabutyl titanate, zinc acetate, sulfuric acid, phosphoric acid, metatitanic acid orthocarbonate, tosic acid, methylsulfonic acid.
6. the preparation method of a kind of flame-retardant hyperbranched polymer according to claim 1 is characterized in that: described organic solvent is one or more the mixed solvent in toluene, dimethylbenzene, dimethyl formamide, the N,N-DIMETHYLACETAMIDE.
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| CN101475683B true CN101475683B (en) | 2011-01-26 |
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|---|---|---|---|---|
| CN101914208B (en) * | 2010-08-19 | 2012-07-25 | 中国科学技术大学 | Phosphorus-containing and nitrogen-containing expansion type flame-retardant polymer and preparation method thereof |
| CN103881076B (en) * | 2014-03-07 | 2016-03-02 | 济南大学 | A kind of preparation method of Halogen hyperbranched expandable type fire retardant |
| TWI506085B (en) | 2014-12-31 | 2015-11-01 | Ind Tech Res Inst | Resin composition and coating material using the same |
| US9670312B2 (en) * | 2015-02-26 | 2017-06-06 | International Business Machines Corporation | Flame-retardant polymers derived from polyols and polyacids |
| CN115584097B (en) * | 2022-08-31 | 2024-02-27 | 湖北金牛管业有限公司 | CPVC power cable conduit and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182375A (en) * | 2007-12-07 | 2008-05-21 | 中南民族大学 | Preparation of nitrogen hyper branched polyphosphate ester |
| US20080269384A1 (en) * | 2004-09-04 | 2008-10-30 | Hans-Dieter Naegerl | Polyphosphate Derivative of a 1,3,5-Triazine Compound, Method for Producing the Same and its Use |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080269384A1 (en) * | 2004-09-04 | 2008-10-30 | Hans-Dieter Naegerl | Polyphosphate Derivative of a 1,3,5-Triazine Compound, Method for Producing the Same and its Use |
| CN101182375A (en) * | 2007-12-07 | 2008-05-21 | 中南民族大学 | Preparation of nitrogen hyper branched polyphosphate ester |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2007-99901A 2007.04.19 |
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Address after: Beishe Yucai Road 215214 Wujiang city Jiangsu province FENHU Economic Development Zone No. 36 Patentee after: SUZHOU HYPERT RESIN SCIENCE & TECHNOLOGY Co.,Ltd. Patentee after: SUZHOU TAIHU ELECTRIC ADVANCED MATERIAL Co.,Ltd. Address before: Beishe Yucai Road 215214 Wujiang city Jiangsu province FENHU Economic Development Zone No. 36 Patentee before: SUZHOU HYPERT RESIN SCIENCE & TECHNOLOGY Co.,Ltd. Patentee before: Wujiang Taihu Insulation Materials Co.,Ltd. Address after: Beishe Yucai Road 215214 Wujiang city Jiangsu province FENHU Economic Development Zone No. 36 Patentee after: SUZHOU HYPERT RESIN SCIENCE & TECHNOLOGY Co.,Ltd. Patentee after: Wujiang Taihu Insulation Materials Co.,Ltd. Address before: Beishe Yucai Road 215214 Wujiang city Jiangsu province FENHU Economic Development Zone No. 36 Patentee before: SUZHOU HYPERT RESIN SCIENCE & TECHNOLOGY Co.,Ltd. Patentee before: Wujiang Taihu Insulating Material Factory |