CN107286321A - The preparation method of environment-friendly type brominated epoxy resin high polymer - Google Patents
The preparation method of environment-friendly type brominated epoxy resin high polymer Download PDFInfo
- Publication number
- CN107286321A CN107286321A CN201710406446.8A CN201710406446A CN107286321A CN 107286321 A CN107286321 A CN 107286321A CN 201710406446 A CN201710406446 A CN 201710406446A CN 107286321 A CN107286321 A CN 107286321A
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- CN
- China
- Prior art keywords
- epoxy resin
- brominated epoxy
- high polymer
- environment
- friendly type
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of environment-friendly type brominated epoxy resin high polymer.Brominated epoxy resin oligomer is dissolved in toluene by the present invention, is configured to mixed solution；After the mixed solution is delivered to industrial chromatographic column purification through pump；Mixed solution is delivered to toluene distillation in reactor；Under conditions of nitrogen circulation, after brominated epoxy resin oligomer sterling is mixed with tetrabromobisphenol A, tribromphenol in proportion, composite catalyst is added, 1~2h is reacted；At 220~230 DEG C, catalyst is added, 1~2h is reacted under vacuum；It is passed through after nitrogen, places HMW brominated epoxy resin under conditions of nitrogen circulation in charging tray.The present invention greatly improves molecular weight, fusing point, toughness and the impact resistance of traditional brominated epoxy resin；The product has higher bromine content, excellent heat endurance and ultraviolet-resistent property；The residual volume of tetrabromobisphenol A can be down to below 5ppm simultaneously, product was both filled the domestic gaps, and International Environmental Protection requirement is reached again.
Description
Technical field
The present invention relates to a kind of preparation method of environment-friendly type brominated epoxy resin high polymer, belong to organic polymer synthesis skill
Art field.
Background technology
Brominated epoxy resin is because of its good excellent heat endurance, resistance to heat aging and processing characteristics, particularly anti-purple
Outside line performance is splendid be widely applied with engineering plastic modification material., can be to brominated epoxy due to the presence of epoxide group
The molecular weight of resin is designed.The brominated epoxy resin of different molecular weight, its fusing point, toughness, impact resistance and heat endurance
It is different etc. performance, so as to cause application field different.Existing domestic commercially available brominated epoxy resin molecular weight is probably distributed in 656
~25000 or so, used in the modifying plastics such as PCB (copper-clad plate), ABS, HIPS, ABS/PC high polymer and PBT, but because of it
Toughness and impact resistance deficiency are in nylon 6 and nylon66 fiber using less.Simultaneously with the enhancing of social environment consciousness, to tetrabromo
There is larger dispute in the use of bisphenol-A, therefore how to reduce the content of tetrabromobisphenol A in brominated epoxy resin as a weight
The problem wanted.
Domestic relevant report：Shandong Tianyi Chemical Co., Ltd. (Chinese patent CN201410266679.9) and open U.S.
Chemical science and technology (Nantong) Co., Ltd (Chinese patent CN201010154179.8) is using tetrabromobisphenol A and epoxychloropropane as original
After material production brominated epoxy resin oligomer, pass through polymerisation and tetrabromobisphenol A synthetic molecular weight (Mw：20000~25000)
Brominated epoxy resin, wherein tetrabromobisphenol A residual volume be less than 100ppm.The problem of for tetrabromobisphenol A residual volume, does not solve also
Certainly.
Molecular weight (the MW that this patent is related to：180000~220000), tetrabromobisphenol A residual volume≤5ppm, high tenacity and
The brominated epoxy resin production technology of high impact properties has not been reported.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of preparation method of environment-friendly type brominated epoxy resin high polymer,
This method of the invention can greatly improve molecular weight, fusing point, toughness and the impact resistance of traditional brominated epoxy resin；The product has
Higher bromine content, excellent heat endurance and ultraviolet-resistent property；The residual volume of tetrabromobisphenol A can be down to below 5ppm simultaneously,
Product was both filled the domestic gaps, and International Environmental Protection requirement is reached again.
The present invention is achieved by the following technical solutions：
The invention provides a kind of preparation method of environment-friendly type brominated epoxy resin high polymer, it comprises the following steps：
Brominated epoxy resin oligomer, tetrabromobisphenol A and tribromphenol are mixed to clarification at 140~160 DEG C, plus
Enter composite catalyst, prepolymerization is carried out at 220~250 DEG C, prepolymer is obtained；
By the prepolymer under the catalysis of single catalyst, polymerisation is carried out in 220~250 DEG C, the ring is obtained
Guarantor's type brominated epoxy resin high polymer.
Preferably, the mass ratio of the brominated epoxy resin oligomer, tetrabromobisphenol A and tribromphenol is 1：
(0.82~0.85)：(0.02~0.03).
Preferably, the mass ratio of the brominated epoxy resin oligomer and composite catalyst is 1：(0.004~
0.006)。
Preferably, the polymerisation is under -0.08~-0.09Mpa vacuum condition in relative degree of vacuum
Carry out.
Preferably, the composite catalyst is triethylamine hydrochloride, benzyltriethylammonium chloride and three [2.4- bis-
Tert-butyl-phenyl] phosphite mixture.
Preferably, the triethylamine hydrochloride, benzyltriethylammonium chloride and three [2.4- di-tert-butyl-phenyls]
The mass ratio of phosphite ester is (1~1.5)：1：(2~2.5).
Preferably, the mass ratio of the brominated epoxy resin oligomer and single catalyst is 1：(0.004~
0.006)。
Preferably, the single catalyst is 1- vinyl imidazoles.
Preferably, the brominated epoxy resin oligomer is first purified, the purifying before prepolymerization is carried out
The step of be：
It is 1 in mass ratio by brominated epoxy resin oligomer and toluene：(0.6~0.7) throw and mixing is generated into mixing kettle
Solution, is delivered to industrial chromatographic column through gear pump and is purified, the mixed solution after purification is delivered in reactor, toluene distillation
It is extremely dry.
Preferably, the industrial chromatographic column is the stainless steel chromatographic column filled with hi-sil, the silica gel
The mesh number of glue is 200~300 mesh；The mixing kettle is stainless steel recycle oil kneader.
Compared with prior art, the present invention has following beneficial effect：
The present invention provides the preparation method of environment-friendly type brominated epoxy resin high polymer, using industrial chromatographic column to brominated epoxy
Resin oligomer is purified, and the brominated epoxy resin oligomer that molecular weight is 656~657 is obtained, so as to accurately control bromine
Change the molecular weight ranges of epoxy resin high polymer；Using composite catalyst control reaction process cause reactant viscosity at the uniform velocity on
Rise, while preventing product from aoxidizing；Brominated epoxy resin high polymer is blocked using addition tribromphenol, product heat can be improved
Stability；Enough heats and power of agitator can be provided using stainless steel recycle oil kneader；Using 1- vinyl imidazoles as urging
Agent, so as to improve toughness of products and impact resistance；React, removed completely simultaneously in reduction product viscosity using under vacuum condition
The tribromphenol remained in product；Using the residual quantity of extension reaction time reduction tetrabromobisphenol A and tribromphenol.
The present invention compared with prior art, employs brominated epoxy resin high polymer synthetic method, from more rational
Material matching, production technology and novel composite catalyst, the molecular weight product control of production is 180000~220000, and tetrabromo is double
Phenol a contents≤5ppm, fusing point is 205~225 DEG C；Product was both filled the domestic gaps, and International Environmental Protection requirement is reached again.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
It is 1 in mass ratio by brominated epoxy resin oligomer and toluene：0.6 throwing generates mixed solution into mixing kettle, passes through
Gear pump is delivered to industrial chromatographic column and purified, and the mixed solution after purification is delivered in reactor, and toluene distillation is to dry；
By brominated epoxy resin oligomer, tetrabromobisphenol A and tribromphenol after purification mixed at 140~160 DEG C to
After clarification, composite catalyst is added, prepolymerization is carried out at 220~250 DEG C, prepolymer is obtained；
By the prepolymer under the catalysis of single catalyst, polymerisation is carried out in 220~250 DEG C, the ring is obtained
Guarantor's type brominated epoxy resin high polymer.
The mass ratio of the brominated epoxy resin oligomer, tetrabromobisphenol A and tribromphenol is 1：0.82：0.03.
The mass ratio of the brominated epoxy resin oligomer and composite catalyst is 1：0.004.
The polymerisation is carried out in the case where relative degree of vacuum is -0.08~-0.09Mpa vacuum condition.
The composite catalyst is that triethylamine hydrochloride, benzyltriethylammonium chloride and three [2.4- di-tert-butyl-phenyls] are sub-
Phosphate mixture.
The quality of the triethylamine hydrochloride, benzyltriethylammonium chloride and three [2.4- di-tert-butyl-phenyls] phosphite esters
Than for 1：1：2.
The mass ratio of the brominated epoxy resin oligomer and single catalyst is 1：0.004.
The single catalyst is 1- vinyl imidazoles.
The industrial chromatographic column is the stainless steel chromatographic column filled with hi-sil, and the mesh number of the hi-sil is 200
~300 mesh；The mixing kettle is stainless steel recycle oil kneader.
Embodiment 2
It is 1 in mass ratio by brominated epoxy resin oligomer and toluene：0.65 throwing generates mixed solution into mixing kettle, passes through
Gear pump is delivered to industrial chromatographic column and purified, and the mixed solution after purification is delivered in reactor, and toluene distillation is to dry；
By brominated epoxy resin oligomer, tetrabromobisphenol A and tribromphenol after purification mixed at 140~160 DEG C to
After clarification, composite catalyst is added, prepolymerization is carried out at 220~250 DEG C, prepolymer is obtained；
By the prepolymer under the catalysis of single catalyst, polymerisation is carried out in 220~250 DEG C, the ring is obtained
Guarantor's type brominated epoxy resin high polymer.
The mass ratio of the brominated epoxy resin oligomer, tetrabromobisphenol A and tribromphenol is 1：0.85：0.02.
The mass ratio of the brominated epoxy resin oligomer and composite catalyst is 1：0.005.
The polymerisation is carried out in the case where relative degree of vacuum is -0.08~-0.09Mpa vacuum condition.
The composite catalyst is that triethylamine hydrochloride, benzyltriethylammonium chloride and three [2.4- di-tert-butyl-phenyls] are sub-
Phosphate mixture.
The quality of the triethylamine hydrochloride, benzyltriethylammonium chloride and three [2.4- di-tert-butyl-phenyls] phosphite esters
Than for 1.5：1：2.5.
The mass ratio of the brominated epoxy resin oligomer and single catalyst is 1：0.005.
The single catalyst is 1- vinyl imidazoles.
The industrial chromatographic column is the stainless steel chromatographic column filled with hi-sil, and the mesh number of the hi-sil is 200
~300 mesh；The mixing kettle is stainless steel recycle oil kneader.
Embodiment 3
It is 1 in mass ratio by brominated epoxy resin oligomer and toluene：0.7 throwing generates mixed solution into mixing kettle, passes through
Gear pump is delivered to industrial chromatographic column and purified, and the mixed solution after purification is delivered in reactor, and toluene distillation is to dry；
By brominated epoxy resin oligomer, tetrabromobisphenol A and tribromphenol after purification mixed at 140~160 DEG C to
After clarification, composite catalyst is added, prepolymerization is carried out at 220~250 DEG C, prepolymer is obtained；
By the prepolymer under the catalysis of single catalyst, polymerisation is carried out in 220~250 DEG C, the ring is obtained
Guarantor's type brominated epoxy resin high polymer.
The mass ratio of the brominated epoxy resin oligomer, tetrabromobisphenol A and tribromphenol is 1：0.84：0.025.
The mass ratio of the brominated epoxy resin oligomer and composite catalyst is 1：0.006.
The polymerisation is carried out in the case where relative degree of vacuum is -0.08~-0.09Mpa vacuum condition.
The composite catalyst is that triethylamine hydrochloride, benzyltriethylammonium chloride and three [2.4- di-tert-butyl-phenyls] are sub-
Phosphate mixture.
The quality of the triethylamine hydrochloride, benzyltriethylammonium chloride and three [2.4- di-tert-butyl-phenyls] phosphite esters
Than for 1.5)：1：2.
The mass ratio of the brominated epoxy resin oligomer and single catalyst is 1：0.006.
The single catalyst is 1- vinyl imidazoles.
The industrial chromatographic column is the stainless steel chromatographic column filled with hi-sil, and the mesh number of the hi-sil is 200
~300 mesh；The mixing kettle is stainless steel recycle oil kneader.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. a kind of preparation method of environment-friendly type brominated epoxy resin high polymer, it is characterised in that comprise the following steps：
Brominated epoxy resin oligomer, tetrabromobisphenol A and tribromphenol are mixed to clarification at 140~160 DEG C, added multiple
Catalyst is closed, prepolymerization is carried out at 220~250 DEG C, prepolymer is obtained；
By the prepolymer under the catalysis of single catalyst, polymerisation is carried out in 220~250 DEG C, the environment-friendly type is obtained
Brominated epoxy resin high polymer.
2. the preparation method of environment-friendly type brominated epoxy resin high polymer as claimed in claim 1, it is characterised in that the bromination
The mass ratio of epoxy resin oligomer, tetrabromobisphenol A and tribromphenol is 1：(0.82~0.85)：(0.02~0.03).
3. the preparation method of environment-friendly type brominated epoxy resin high polymer as claimed in claim 1, it is characterised in that the bromination
The mass ratio of epoxy resin oligomer and composite catalyst is 1：(0.004~0.006).
4. the preparation method of environment-friendly type brominated epoxy resin high polymer as claimed in claim 1, it is characterised in that the polymerization
Reaction is carried out in the case where relative degree of vacuum is -0.08~-0.09Mpa vacuum condition.
5. the preparation method of environment-friendly type brominated epoxy resin high polymer as claimed in claim 1, it is characterised in that described compound
Catalyst is triethylamine hydrochloride, benzyltriethylammonium chloride and three [2.4- di-tert-butyl-phenyls] phosphite mixtures.
6. the preparation method of environment-friendly type brominated epoxy resin high polymer as claimed in claim 5, it is characterised in that three second
The mass ratio of amine hydrochlorate, benzyltriethylammonium chloride and three [2.4- di-tert-butyl-phenyls] phosphite esters is (1~1.5)：1：
(2~2.5).
7. the preparation method of environment-friendly type brominated epoxy resin high polymer as claimed in claim 1, it is characterised in that the bromination
The mass ratio of epoxy resin oligomer and single catalyst is 1：(0.004~0.006).
8. the preparation method of the environment-friendly type brominated epoxy resin high polymer as described in claim 1 or 7, it is characterised in that described
Single catalyst is 1- vinyl imidazoles.
9. the preparation method of environment-friendly type brominated epoxy resin high polymer as claimed in claim 1, it is characterised in that the bromination
Epoxy resin oligomer is first purified before prepolymerization is carried out, and is the step of the purifying：
It is 1 in mass ratio by brominated epoxy resin oligomer and toluene：(0.6~0.7) throw and mixed solution generated into mixing kettle,
Industrial chromatographic column is delivered to through gear pump to be purified, the mixed solution after purification is delivered in reactor, toluene distillation is to dry.
10. the preparation method of environment-friendly type brominated epoxy resin high polymer as claimed in claim 9, it is characterised in that the work
Industry chromatographic column is the stainless steel chromatographic column filled with hi-sil, and the mesh number of the hi-sil is 200~300 mesh；It is described mixed
Conjunction kettle is stainless steel recycle oil kneader.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710406446.8A CN107286321A (en) | 2017-06-02 | 2017-06-02 | The preparation method of environment-friendly type brominated epoxy resin high polymer |
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| CN201710406446.8A CN107286321A (en) | 2017-06-02 | 2017-06-02 | The preparation method of environment-friendly type brominated epoxy resin high polymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041507A (en) * | 2019-05-07 | 2019-07-23 | 安徽美佳新材料股份有限公司 | A kind of preparation method of environmental protection UV resistance linear epoxy resin |
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| CN101831052A (en) * | 2010-04-23 | 2010-09-15 | 开美化学科技(南通)有限公司 | Production method of low-residue tetrabromobisphemol A brominated epoxy resin |
| CN103553887A (en) * | 2013-10-11 | 2014-02-05 | 镇江市高等专科学校 | Method for preparing bisphenol A-type fire retardant epoxy resin |
| 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 |
| CN104017171A (en) * | 2014-06-16 | 2014-09-03 | 山东天一化学股份有限公司 | Production method of high-thermal-stability brominated epoxy resin |
| CN104961882A (en) * | 2015-06-05 | 2015-10-07 | 朱卫东 | Production method of brominated epoxy resin flame retardant |
| CN106008922A (en) * | 2016-06-22 | 2016-10-12 | 柳州市强威锻造厂 | Brominated epoxy resin curing formula |
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2017
- 2017-06-02 CN CN201710406446.8A patent/CN107286321A/en active Pending
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| CN101831052A (en) * | 2010-04-23 | 2010-09-15 | 开美化学科技(南通)有限公司 | Production method of low-residue tetrabromobisphemol A brominated epoxy resin |
| CN103553887A (en) * | 2013-10-11 | 2014-02-05 | 镇江市高等专科学校 | Method for preparing bisphenol A-type fire retardant epoxy resin |
| 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 |
| CN104017171A (en) * | 2014-06-16 | 2014-09-03 | 山东天一化学股份有限公司 | Production method of high-thermal-stability brominated epoxy resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110041507A (en) * | 2019-05-07 | 2019-07-23 | 安徽美佳新材料股份有限公司 | A kind of preparation method of environmental protection UV resistance linear epoxy resin |
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