CN1115577A - Process for producing a high molecular weight epoxy resin - Google Patents
Process for producing a high molecular weight epoxy resin Download PDFInfo
- Publication number
- CN1115577A CN1115577A CN94190789A CN94190789A CN1115577A CN 1115577 A CN1115577 A CN 1115577A CN 94190789 A CN94190789 A CN 94190789A CN 94190789 A CN94190789 A CN 94190789A CN 1115577 A CN1115577 A CN 1115577A
- Authority
- CN
- China
- Prior art keywords
- epoxy
- high molecular
- molecular weight
- epoxy resin
- requirement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
-
- 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
- C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
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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)
- Polyethers (AREA)
Abstract
The invention discloses a method that can prepare epoxy resin with high molecular weight in a short time, which leads the epoxy resin, each molecule of which averagely contains epoxy groups that is more than one but less than three, to react with dihydric phenol compound, each molecule of which averagely contains phenolic hydroxyl groups that is more than one but less than three. The invention is characterized in that the reaction is carried out without the presence of primary hydroxyl glycol ether solvent.
Description
The present invention relates to be used for the preparation method of the high molecular expoxy resin of tackiness agent, barrier material, lacquer and other coating, moulding product etc., particularly relate to the method that can prepare high molecular expoxy resin within a short period of time.
High molecular expoxy resin is by the prepared in reaction of low-molecular-weight bifunctional Resins, epoxy and dihydric phenolic compounds.This method is commonly referred to as " chain extension method (advancementprocess) ".For example Japanese patent gazette 28-4494 discloses a kind of chain extension method, and it is a kind of polymerization process that does not have solvent.But the molecular-weight average of the resin behind the chain extension that makes with this method only has an appointment 11,000.
Other uses solvent to carry out polymeric chain extension rule as being disclosed in Japanese Patent Application Publication 04-12124,54-52200,60-118757,60-144323 and 60-114324, in these methods, the preferred solvent that uses comprises methylethylketone, methyl iso-butyl ketone (MIBK), hexanaphthene, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether and N, N-N,N-DIMETHYLACETAMIDE.
But, use as the low boiling point solvent of methylethylketone when preparing high molecular expoxy resin, because temperature of reaction can not be too high, so the reaction times is very long, and a large amount of catalyzer of needs.Use as glycol ethyl ether, ethylene glycol butyl ether or N, during the high boiling solvent of N-N,N-DIMETHYLACETAMIDE, polyreaction can at high temperature be carried out, thereby can shorten the reaction times to a certain extent.But, consider that from productivity hope can obtain the high-molecular weight polymerisate in the shorter time.
The purpose of this invention is to provide ten thousand methods of using the very little solvent of toxicity to prepare high molecular expoxy resin at short notice.
For addressing the above problem, the present inventor discovers, with respect to ether group or other hydroxyl, contain primary hydroxyl glycol ethers can with the epoxy reaction in the Resins, epoxy, this reaction terminating the chainpropagation of Resins, epoxy, can not obtain high molecular weight product.
Therefore, the invention provides the method for preparing high molecular expoxy resin, it contains more than 1 and the Resins, epoxy that is less than 3 epoxy group(ing) and (2) average per molecule (1) average per molecule to contain more than 1 and be less than the dihydric phenolic compounds reaction of 3 phenolic hydroxyl groups, it is characterized in that this is reflected under the existence of no primary hydroxyl glycol ether solvent and carries out.
The present invention is described in more detail below.
The Resins, epoxy (below be called bifunctional Resins, epoxy) that is used for the present invention comprises that average per molecule contains more than 1 and is less than any compound of 3 epoxy group(ing).The epoxy group(ing) number of average per molecule be preferably more than 1.8 and be less than 3, more preferably less than 2.1, be most preferably 2.Bifunctional Resins, epoxy for example comprises the diglycidyl ether of diglycidyl ether, the dibasic alcohol of dihydroxyphenyl propane based epoxy resin, Bisphenol F based epoxy resin, dihydroxyphenyl propane D based epoxy resin, bisphenol S based epoxy resin, cycloaliphatic epoxy resin, fatty linear epoxy resin, dihydric phenol, their halogenide, their hydride or the like.Described Resins, epoxy can use or mix use separately.In described Resins, epoxy, preferred Resins, epoxy comprises dihydroxyphenyl propane based epoxy resin and Bisphenol F based epoxy resin.In addition, except that above-mentioned bifunctional Resins, epoxy, only otherwise influence the performance that product is wished, also can contain other epoxide component in the reaction mixture, as a spot of epoxy-Novolak resin.
In the present invention, as the Resins, epoxy of raw material usually (but not must) be the lower Resins, epoxy of molecular weight.The epoxy equivalent (weight) of bifunctional Resins, epoxy is preferably 170-400, and more preferably 175-250.Its number-average molecular weight is preferably 340-1000, and more preferably 350-500.In the present invention, as commercial Resins, epoxy, for example can use D.E.R
331L, D.E.R
383J, D.E.R
661 (commodity of Dow Chemveal Company).
In the present invention, can be on average to contain more than 1 and be less than 3, preferred 1.8-2.1, any phenolic compound of 2 phenolic hydroxyl groups most preferably from about as the dihydric phenol of the polymerization chainextender of Resins, epoxy.Dihydric phenol for example comprises: the monocycle dihydric phenol, as Resorcinol, Resorcinol and pyrocatechol; Many ring dihydric phenols are as dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S; Their halide derivative; Their alkyl-substituted derivative; Or the like.Above-claimed cpd can use or mix use separately.In above-mentioned dihydric phenolic compounds, the phenol that preferably uses among the present invention is dihydroxyphenyl propane and Bisphenol F.In addition, except that above-mentioned dihydric phenol, only otherwise influence the performance that product is wished, also can contain other phenol component in the reaction mixture, as novolac resin or trihydric phenol.
The equivalence ratio of epoxy group(ing) and phenolic hydroxyl group is generally 0.7-1.4: 1, is preferably 0.9-1.1: 1.If this equivalence ratio is less than 0.7 or greater than 1.4, the imbalance on this stoichiometry will cause the molecular weight of product to reduce.
In the present invention, solvent contains does not have primary hydroxyl in the molecule, promptly be connected in the glycol ethers of the hydroxyl on the primary carbon atom.Glycol ethers comprises 1, the 2-propylene glycol that has hydroxyl on the β position.The raw material of this propylene glycol solubilized such as Resins, epoxy and phenol, they for example comprise acetic ester, 1,2-propylene glycol propyl ether, 1,2-propylene glycol single-butyl ether of 1,2-methyl proxitol, 1,2-methyl proxitol etc.Preferred 1,2-propylene glycol single-butyl ether.
The boiling point of glycol ether solvent preferably is higher than 140 ℃, more preferably is higher than 165 ℃.To the upper limit of boiling point without limits, but preferably be not higher than 300 ℃.In order to dissolve the resin behind the chain extension, after finishing, chain extension can add another kind of solvent, as ketone, acid amides, ether or aromatic hydrocarbons.
The consumption of solvent preferably accounts for 10%-50% of reaction mixture amount, and more preferably 20%-40%.If solvent load is lower than 10%, the viscosity of resin is increased to the degree that is difficult to stir very soon.On the other hand, if solvent load is higher than 50%, speed of response will be too low.
Polyreaction of the present invention is preferably carried out under the condition of using catalyzer.Catalyzer for example comprises: imidazoles, as 2-Methylimidazole; Tertiary amine is as triethylamine, tripropyl amine and Tributylamine; Phosphonium salt is as Yi base triphenyl phosphonium muriate, Yi base triphenyl phosphonium bromide and Yi base triphenyl phosphonium acetate; Ammonium salt is as phenmethyl trimethyl ammonium muriate and phenmethyl trimethyl ammonium oxyhydroxide.The suitable catalyzer that the present invention uses is the high activated catalyst that can at high temperature use, preferred phosphorus-containing catalyst, and Te other Shi phosphonium salt is as Yi base triphenyl phosphonium acetate.Based on the reaction reagent solid weight, catalyst consumption is preferably 0.001%-10%, and more preferably 0.01%-5%.If the Resins, epoxy behind the chain extension is intended to be used for the coating of food box, catalyst consumption is preferably lower than 0.25% weight.
In the present invention, polyreaction is carried out under higher temperature, and this temperature is lower than the boiling point of polymerization solvent, and is lower than the decomposition temperature of polymerizing catalyst.Temperature of reaction is preferably 100 ℃-250 ℃, more preferably 120 ℃-200 ℃.Reaction times is preferably 1-12 hours, more preferably 3-7 hours.Polyreaction can be under normal pressure, high pressure or decompression, carry out with continuous or intermittent mode.
The molecular-weight average of the chain-extened epoxy resin that the inventive method makes is 20,000-200,000, more preferably 50,000-150,000.The molecular weight distribution of the resin behind the chain extension (Mw/Mn) is preferably 2-15, preferred 4-11.In addition, under preferred condition, use preferred reagent, adopt the inventive method in 3-7 hours, can make the Resins, epoxy of weight-average molecular weight greater than 50,000 (more preferably greater than 70,000).
The high molecular expoxy resin that the inventive method makes can be used as tackiness agent, barrier material, molding solution and powder coating etc., is preferably used as lacquer, more preferably is used as the lacquer of coating metal box.
Embodiment
The following example is used to illustrate in greater detail the present invention, and in an embodiment, " part " is " weight part ".
Embodiment 1-2 and comparative example A-D
Preparation contains the series reaction mixture of following component:
(1) liquid epoxies of the amount of Table 1, its epoxy equivalent (weight) are about 180,
(2) dihydroxyphenyl propane of the amount of Table 1,
(3) phosphate catalyst of the Yi of about 0.18% (based on resin solid weight) base triphenyl phosphonium and
(4) solvent shown in the table 1.
At about 170 ℃, make each reaction mixture reaction 4-7 hours.Resin sample behind the taking-up chain extension is measured weight-average molecular weight with gel permeation chromatography (is reference with the polystyrene), and table 1 shows the result.Comparative Examples is not embodiment of the present invention.
Table 1
| Embodiment 1 | The comparative example A | Comparative Examples B | Comparative Examples C | Embodiment 2 | Comparative Examples D | |
| LER (part) B15-A (part) PnB (part) EB (part) DE (part) DMAC (part) ETPPA (%) ETPPP (%) reaction temperature (℃) molecular weight (4 hours) molecular weight (7 hours) | ???431 ???269 ???300 ???0.18 ???170 ???129,000 ????— | ????431 ????269 ????300 ????0.18 ????170 ????56,000 ?????— | ????431 ????269 ????300 ????0.18 ????170 ????56,000 ????67,000 | ????433 ????267 ????300 ????0.18 ????150 ????45,000 ?????— | ????433 ????267 ????300 ????0.18 ????170 ????50,000 ????72,000 | ????309 ????191 ????500 ????0.18 ????150 ????17,000 ????24,000 |
Following compounds is represented in abbreviation in the table
LER: dihydroxyphenyl propane based epoxy resin
BIS-A: dihydroxyphenyl propane
PnB:1,2-propylene glycol single-butyl ether
ETPPA: Yi base triphenyl phosphonium acetate
ETPPP: Yi base triphenyl phosphonium phosphoric acid salt
Evaluation result
Comparing embodiment 1 and comparative example A-D as can be seen, according to the present invention, polymerization can obtain molecular weight in 4 hours up to 129,000 product.But identical in other condition, have only under the different condition of solvent, it is 45,000-56,000 product that comparative example A-C can only obtain molecular weight.Therefore as can be seen, under the reaction conditions identical with currently known methods, the inventive method can make the product that molecular weight improves greatly.
Comparing embodiment 2 and Comparative Examples D as can be seen, under identical reaction conditions, even use active lower Yi base triphenyl phosphonium phosphate catalyst, the weight-average molecular weight of the product that embodiment 2 obtains still is about 3 times of Comparative Examples D.Therefore prove that under the reaction conditions identical with currently known methods, the inventive method can make the product that molecular weight improves greatly.
As mentioned above, compare with the prior art method of using polymer solvent commonly used, the inventive method can make the more epoxy resin of HMW at short notice.
Claims (9)
1. the method for preparing high molecular expoxy resin, it contains more than 1 and the Resins, epoxy that is less than 3 epoxy group(ing) and (2) average per molecule (1) average per molecule to contain more than 1 and be less than the dihydric phenolic compounds reaction of 3 phenolic hydroxyl groups, it is characterized in that this is reflected under the existence of no primary hydroxyl glycol ether solvent and carries out.
2. according to the process of claim 1 wherein, described glycol ethers is 1,2-propylene glycol.
3. according to the method for claim 2, wherein, described glycol ethers is 1,2-propylene glycol single-butyl ether.
4. according to the method for each requirement in the claim 1 to 3, wherein, this is reflected under the catalyzer existence and carries out.
5. according to the method for each requirement in the claim 1 to 3, wherein, this is reflected at P contained compound and does to carry out under the existence of catalyzer.
6. according to the method for each requirement in the claim 1 to 3, wherein, this is reflected under 120 ℃-200 ℃ the temperature and carries out.
7. according to the method for each requirement in the claim 1 to 3, wherein, this is reflected under 120 ℃-200 ℃ the temperature, carries out in the presence of catalyzer.
8. according to the method for each requirement in the claim 1 to 3, wherein, this is reflected under 120 °-200 ° the temperature, P contained compound do catalyzer in the presence of carry out.
9. the high molecular expoxy resin that makes of the method for claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5280666A JPH07109331A (en) | 1993-10-15 | 1993-10-15 | Method for producing high molecular weight epoxy resin |
| JP280666/93 | 1993-10-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1115577A true CN1115577A (en) | 1996-01-24 |
Family
ID=17628246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94190789A Pending CN1115577A (en) | 1993-10-15 | 1994-10-06 | Process for producing a high molecular weight epoxy resin |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0677073A1 (en) |
| JP (1) | JPH07109331A (en) |
| KR (1) | KR950704391A (en) |
| CN (1) | CN1115577A (en) |
| AU (1) | AU7930194A (en) |
| BR (1) | BR9406155A (en) |
| CA (1) | CA2151745A1 (en) |
| CZ (1) | CZ156295A3 (en) |
| PL (1) | PL309390A1 (en) |
| RU (1) | RU95113592A (en) |
| WO (1) | WO1995010556A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103140534A (en) * | 2010-09-30 | 2013-06-05 | 陶氏环球技术有限责任公司 | Coating compositions |
| CN109897528A (en) * | 2019-02-14 | 2019-06-18 | 安庆北化大科技园有限公司 | A kind of modified coating and the preparation method and application thereof |
| CN112250836A (en) * | 2020-12-08 | 2021-01-22 | 北京市银帆涂料有限责任公司 | High molecular compound, coating composition containing high molecular compound and preparation method of coating composition |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3657720B2 (en) * | 1996-12-11 | 2005-06-08 | ジャパンエポキシレジン株式会社 | Method for producing polymer epoxy resin |
| JP2006036801A (en) * | 2004-07-22 | 2006-02-09 | Japan Epoxy Resin Kk | High-molecular weight epoxy resin composition, film obtained using the same and cured product of the same |
| CN103140532B (en) | 2010-09-30 | 2016-05-04 | 蓝立方知识产权有限责任公司 | Epoxy resin adduct and thermosets thereof |
| EP2621994A1 (en) | 2010-09-30 | 2013-08-07 | Dow Global Technologies LLC | Epoxy resin compositions |
| BR112013007037A2 (en) | 2010-09-30 | 2019-09-24 | Dow Global Technologies Llc | thermosetting resin composition, partially cured product, fully cured thermoset product, process for preparing a thermosetting composition, process for curing a mixture composition and article |
| WO2012044442A1 (en) | 2010-09-30 | 2012-04-05 | Dow Global Technologies Llc | Process for preparing epoxy resins |
| US10442572B2 (en) | 2014-10-20 | 2019-10-15 | Ppg Industries Ohio, Inc. | Coated food-contacting containers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2205097A1 (en) * | 1971-03-31 | 1972-10-05 | Shell Internationale Research Maatschappij N.V., Den Haag (Niederlande) | Process for the production of polyepoxides |
| US4837293A (en) * | 1987-08-28 | 1989-06-06 | The Dow Chemical Company | Linear bisphenol epoxy polymers containing cyano groups |
| US5310854A (en) * | 1989-08-23 | 1994-05-10 | The Dow Chemical Company | Epoxy resin composition and process therefor |
-
1993
- 1993-10-15 JP JP5280666A patent/JPH07109331A/en active Pending
-
1994
- 1994-10-06 BR BR9406155A patent/BR9406155A/en not_active Application Discontinuation
- 1994-10-06 AU AU79301/94A patent/AU7930194A/en not_active Abandoned
- 1994-10-06 CZ CZ951562A patent/CZ156295A3/en unknown
- 1994-10-06 KR KR1019950702415A patent/KR950704391A/en not_active Application Discontinuation
- 1994-10-06 RU RU95113592/04A patent/RU95113592A/en unknown
- 1994-10-06 CA CA002151745A patent/CA2151745A1/en not_active Abandoned
- 1994-10-06 CN CN94190789A patent/CN1115577A/en active Pending
- 1994-10-06 WO PCT/US1994/011349 patent/WO1995010556A1/en not_active Application Discontinuation
- 1994-10-06 EP EP94930061A patent/EP0677073A1/en not_active Withdrawn
- 1994-10-06 PL PL94309390A patent/PL309390A1/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103140534A (en) * | 2010-09-30 | 2013-06-05 | 陶氏环球技术有限责任公司 | Coating compositions |
| CN103140534B (en) * | 2010-09-30 | 2016-05-11 | 蓝立方知识产权有限责任公司 | Coating composition |
| CN109897528A (en) * | 2019-02-14 | 2019-06-18 | 安庆北化大科技园有限公司 | A kind of modified coating and the preparation method and application thereof |
| CN112250836A (en) * | 2020-12-08 | 2021-01-22 | 北京市银帆涂料有限责任公司 | High molecular compound, coating composition containing high molecular compound and preparation method of coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9406155A (en) | 1996-01-30 |
| KR950704391A (en) | 1995-11-20 |
| AU7930194A (en) | 1995-05-04 |
| WO1995010556A1 (en) | 1995-04-20 |
| EP0677073A1 (en) | 1995-10-18 |
| CZ156295A3 (en) | 1995-12-13 |
| CA2151745A1 (en) | 1995-04-20 |
| PL309390A1 (en) | 1995-10-02 |
| JPH07109331A (en) | 1995-04-25 |
| RU95113592A (en) | 1997-06-10 |
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