CN101633723A - Production method for brominated epoxy resin and produced brominated epoxy resin - Google Patents
Production method for brominated epoxy resin and produced brominated epoxy resin Download PDFInfo
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- CN101633723A CN101633723A CN200910016470A CN200910016470A CN101633723A CN 101633723 A CN101633723 A CN 101633723A CN 200910016470 A CN200910016470 A CN 200910016470A CN 200910016470 A CN200910016470 A CN 200910016470A CN 101633723 A CN101633723 A CN 101633723A
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Abstract
The invention discloses a production method for brominated epoxy resin and produced brominated epoxy resin, the method comprises the steps that: after tetra bromobisphenol A, brominated epoxy resin oligomer and catalyst are stirred and melted, 9,10-dihydro-9-oxa-10-DOPO-10-oxide is added for reaction to synthesize DOPO-terminated brominated epoxy resin which is DBEO-type brominated epoxy resin with the molecular weight from 1500 to 30000 and the thermal stability not less than 300 DEG C; as the technical solution of the invention is employed, the brominated epoxy resin with the molecular weight from 1500 to 30000 is synthesized and the thermal stability thereof is not less than 300 DEG C, which makes the types of the brominated epoxy resin affluent.
Description
Technical field
The present invention relates to the production of resins technical field, relate in particular to a kind of production method of fire retarding epoxide resin.
Background technology
Brominated epoxy resin has that high workability, weathering resistance are good, do not produce toxic substance during burning, have gratifying melt flow rate and higher flame retarding efficiency, good thermostability and light stability, and can give by the good physical and mechanical properties of ignition resistant substrate, non-blooming.Be widely used in thermoplasticss such as PBT, PET, PP, ABS, PC.
Brominated epoxy resin can be divided into basic, normal, high three kinds usually by molecular weight.Lower molecular weight is suitable for flame-proof ABS and HIPS, and high molecular is fit to ABS/PC superpolymer, PBT and nylon 6,66.Molecular weight ranges is 700～45000, and the resin of various different molecular weights influences the physicals of flame retardant plastics, thermotolerance, shock resistance etc., thereby can select suitable molecular weight according to fire-retardant requirement of difference and melting index.
At present, brominated epoxy resin is divided into EP type and EC type according to the end group difference.The EP type is compared with the EC type, and the former photostabilization is preferable, but bromine content is lower slightly, and fire-retardant ABS and the HIPS of the latter has more excellent shock strength.EC type brominated epoxy resin chemical structural formula is
EP type brominated epoxy resin chemical structural formula is
Summary of the invention
Technical problem to be solved by this invention provides a kind of production method of brominated epoxy resin and the brominated epoxy resin of production.
For solving the problems of the technologies described above, technical scheme of the present invention is: the production method of brominated epoxy resin is after tetrabromo-bisphenol, brominated epoxy resin oligopolymer and catalyzer are stirred fusion, add 9, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-assorted luxuriant and rich with fragrance end capped brominated epoxy resin of the synthetic phosphinylidyne of 10-oxide compound reaction.
Tetrabromo-bisphenol is mixed with brominated epoxy resin oligopolymer 1: 1 in molar ratio～2, the catalyzer that adds relative tetrabromo-bisphenol quality 0.01～10% afterwards, stir fusion at 80～150 ℃, add 9 again, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-10-oxide compound, synthesize the assorted luxuriant and rich with fragrance end capped brominated epoxy resin of phosphinylidyne behind reaction 0.5～5h down at 90～220 ℃, wherein 9, the 10-dihydro-9-oxy is assorted-and the 10-phosphinylidyne is assorted, and phenanthrene-10-oxide compound add-on is the difference of the molal quantity of brominated epoxy resin oligopolymer and tetrabromo-bisphenol.
Described whipping temp is 80～160 ℃.
Described brominated epoxy resin oligopolymer is a molecular weight 700～1000, epoxy equivalent (weight) 0.2～0.31.
Described catalyzer is a kind of in triphenylphosphine, Trimethylamine 99 or the tetramethyl-amine
Described whipping temp is 80～160 ℃, and reaction is to react 0.5～5h down at 90～220 ℃.
Described brominated epoxy resin oligopolymer is a molecular weight 700～1000, epoxy equivalent (weight) 0.2～0.31; The mol ratio of tetrabromo-bisphenol and brominated epoxy resin oligopolymer is 1: 1～2; 9, assorted-10 phosphinylidynes of 10-dihydro-9-oxy are assorted, and phenanthrene-10-oxide compound add-on is the difference of tetrabromo-bisphenol and brominated epoxy resin oligopolymer molal quantity.
Described catalyzer is a kind of in triphenylphosphine, Trimethylamine 99 or the tetramethyl-amine, and consumption is 0.01～10% of a relative tetrabromo-bisphenol quality.
Described brominated epoxy resin is a DBEO type brominated epoxy resin, and its chemical structural formula is
Molecular weight is 1500～30000, thermostability 〉=300 ℃.
Owing to adopted technique scheme, synthetic molecular weight is from the brominated epoxy resin of 1500～30000 molecular weight, and the kind of brominated epoxy resin has been enriched in its thermostability 〉=300 ℃.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Take by weighing tetrabromo-bisphenol 54.4g, add brominated epoxy resin oligopolymer 140g (molecular weight 700 epoxy equivalent (weight)s 0.285),, stir, add catalyzer triphenylphosphine 1g, stir fusion, add DOPO43.2g, 200 ℃ of temperature of reaction at 120 ℃, 2 hours reaction times, blowing, softening temperature 100-110 ℃.
The DOPO end-blocking brominated epoxy resin of producing is a DBEO type brominated epoxy resin, and molecular weight is 1500, thermostability 〉=300 ℃.
Embodiment 2
Take by weighing tetrabromo-bisphenol 54.4g, add brominated epoxy resin oligopolymer 105g (molecular weight 700 epoxy equivalent (weight)s 0.285),, stir, add catalyzer Trimethylamine 99 3g, stir fusion, add DOPO 21.6g, 200 ℃ of temperature of reaction at 110 ℃, 4 hours reaction times, blowing, softening temperature 110-130 ℃.
The DOPO end-blocking brominated epoxy resin of producing is a DBEO type brominated epoxy resin, and molecular weight is 5000, thermostability 〉=300 ℃.
Embodiment 3
Take by weighing tetrabromo-bisphenol 54.4g, add brominated epoxy resin oligopolymer 96g (molecular weight 800 epoxy equivalent (weight)s 0.25),, stir, add catalyzer tetramethyl-amine 1g, stir fusion, add DOPO 8.64g, 200 ℃ of temperature of reaction at 130 ℃, 3 hours reaction times, blowing, softening temperature 130-140 ℃.
The DOPO end-blocking brominated epoxy resin of producing is a DBEO type brominated epoxy resin, and molecular weight is 10000, thermostability 〉=300 ℃.
Embodiment 4
Take by weighing tetrabromo-bisphenol 54.4g, (molecular weight 1000 epoxy equivalent (weight)s 0.2 stir, and add catalyzer triphenylphosphine 3g to add brominated epoxy resin oligopolymer 120g, stir fusion at 140 ℃, add DOPO 8.64g, 200 ℃ of temperature of reaction, 3 hours reaction times, blowing, softening temperature 125-135 ℃.
The DOPO end-blocking brominated epoxy resin of producing is a DBEO type brominated epoxy resin, and molecular weight is 15000, thermostability 〉=300 ℃.
Embodiment 5
Take by weighing tetrabromo-bisphenol 54.4g, add brominated epoxy resin oligopolymer 136g (molecular weight 700 epoxy equivalent (weight)s 0.285), stir, add catalyzer Trimethylamine 99 3g, stir fusion at 120 ℃, add DOPO40.73g, 200 ℃ of temperature of reaction, 3 hours reaction times, blowing, softening temperature 115-125 ℃.
The DOPO end-blocking brominated epoxy resin of producing is a DBEO type brominated epoxy resin, and molecular weight is 20000, thermostability 〉=300 ℃.
Embodiment 6
Take by weighing tetrabromo-bisphenol 54.4g, add brominated epoxy resin oligopolymer 190g (molecular weight 1000 epoxy equivalent (weight)s 0.2), stir, add catalyzer tetramethyl-amine 2g, stir fusion at 160 ℃, add DOPO38.88g, 200 ℃ of temperature of reaction, 4 hours reaction times, blowing, softening temperature 105-115 ℃.
The DOPO end-blocking brominated epoxy resin of producing is a DBEO type brominated epoxy resin, and molecular weight is 30000, thermostability 〉=300 ℃.
Claims (6)
1. the production method of a brominated epoxy resin, it is characterized in that: this method is after tetrabromo-bisphenol, brominated epoxy resin oligopolymer and catalyzer are stirred fusion, add 9, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-assorted luxuriant and rich with fragrance end capped brominated epoxy resin of the synthetic phosphinylidyne of 10-oxide compound reaction.
2. the production method of brominated epoxy resin as claimed in claim 1, it is characterized in that: tetrabromo-bisphenol is mixed with brominated epoxy resin oligopolymer 1: 1 in molar ratio～2, the catalyzer that adds relative tetrabromo-bisphenol quality 0.01～10% afterwards, stir fusion at 80～150 ℃, add 9 again, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-10-oxide compound, synthesize the assorted luxuriant and rich with fragrance end capped brominated epoxy resin of phosphinylidyne behind reaction 0.5～5h down at 90～220 ℃, wherein 9, the 10-dihydro-9-oxy is assorted-and the 10-phosphinylidyne is assorted, and phenanthrene-10-oxide compound add-on is the difference of the molal quantity of brominated epoxy resin oligopolymer and tetrabromo-bisphenol.
3. the production method of brominated epoxy resin as claimed in claim 1, it is characterized in that: described whipping temp is 80～160 ℃.
4. the production method of brominated epoxy resin as claimed in claim 1, it is characterized in that: described brominated epoxy resin oligopolymer is a molecular weight 700～1000, epoxy equivalent (weight) 0.2～0.31.
5. as the production method of the described brominated epoxy resin of the arbitrary claim of claim 1 to 4, it is characterized in that: described catalyzer is a kind of in triphenylphosphine, Trimethylamine 99 or the tetramethyl-amine.
6. brominated epoxy resin, it is characterized in that: described brominated epoxy resin is a DBEO type brominated epoxy resin, and its chemical structural formula is
Molecular weight is 1500～30000, thermostability 〉=300 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200910016470A CN101633723A (en) | 2009-07-04 | 2009-07-04 | Production method for brominated epoxy resin and produced brominated epoxy resin |
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| CN200910016470A CN101633723A (en) | 2009-07-04 | 2009-07-04 | Production method for brominated epoxy resin and produced brominated epoxy resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967268A (en) * | 2010-10-14 | 2011-02-09 | 北京工商大学 | Halogen-free flame-retardant epoxy resin and preparation method thereof |
| CN103923300A (en) * | 2014-04-17 | 2014-07-16 | 开美化学科技(南通)有限公司 | Preparation method of brominated epoxy resin with low bromine content |
| CN105273362A (en) * | 2015-11-12 | 2016-01-27 | 广东生益科技股份有限公司 | Epoxy resin composition and application thereof |
| CN112080107A (en) * | 2020-09-27 | 2020-12-15 | 诸暨企为科技有限公司 | Electronic material and preparation process thereof |
| CN113956617A (en) * | 2021-10-27 | 2022-01-21 | 江苏拜富科技股份有限公司 | Preparation method of high-insulation low-temperature electronic packaging material |
-
2009
- 2009-07-04 CN CN200910016470A patent/CN101633723A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967268A (en) * | 2010-10-14 | 2011-02-09 | 北京工商大学 | Halogen-free flame-retardant epoxy resin and preparation method thereof |
| CN103923300A (en) * | 2014-04-17 | 2014-07-16 | 开美化学科技(南通)有限公司 | Preparation method of brominated epoxy resin with low bromine content |
| CN105273362A (en) * | 2015-11-12 | 2016-01-27 | 广东生益科技股份有限公司 | Epoxy resin composition and application thereof |
| CN105273362B (en) * | 2015-11-12 | 2017-08-29 | 广东生益科技股份有限公司 | A kind of composition epoxy resin and its application |
| CN112080107A (en) * | 2020-09-27 | 2020-12-15 | 诸暨企为科技有限公司 | Electronic material and preparation process thereof |
| CN113956617A (en) * | 2021-10-27 | 2022-01-21 | 江苏拜富科技股份有限公司 | Preparation method of high-insulation low-temperature electronic packaging material |
| WO2022156832A3 (en) * | 2021-10-27 | 2022-09-22 | 江苏拜富科技股份有限公司 | Preparation method for high-insulativity low-temperature electronic packaging material |
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