GB2039489A - Powdered modified epoxy resin - Google Patents
Powdered modified epoxy resin Download PDFInfo
- Publication number
- GB2039489A GB2039489A GB7901725A GB7901725A GB2039489A GB 2039489 A GB2039489 A GB 2039489A GB 7901725 A GB7901725 A GB 7901725A GB 7901725 A GB7901725 A GB 7901725A GB 2039489 A GB2039489 A GB 2039489A
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- GB
- United Kingdom
- Prior art keywords
- epoxy resin
- weight
- parts
- reactor
- components
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
Five parts by weight of an epoxy resin produced from diphenylol propane and epichlorhydrin are reacted with 0.2 to 3.4 (preferably 1 to 3) parts by weight of furfuramide or 3-methyl-5-furylpyrazoline at 140 to 160 DEG C, cooled to at most 30 DEG C and ground to form a powder. The reaction may be carried out in the presence of trifuryl borate as a flame retardant: such powders may be self-extinguishing or non-inflammable. The powders have better storage life (up to 6 months) and blocking resistance (up to 45 days without blocking) than comparable powdered modified epoxy resins.
Description
SPECIFICATION
Method of preparing a powdered modified epoxy resin
The present invention is concerned with the production of powdered modified epoxy resins, which can be used for purposes such as protective coatings (produced by spraying, for example), laminates, foams and mouldings.
The method according to the invention comprises reacting 5 parts by weight of an epoxy resin produced from diphenylol propane (bisphenol A) and epichlorhydrin with 0.2 to 3.4 parts by weight of a nitrogen-containing furan monomer, namely, furfuramide or3 - methyl - 5 - furylpyrazoline at a reaction temperature of 140 to 1600C, followed by cooling to a temperature not exceeding 30"C and grinding to produce a powder.
When the nitrogen-containing furan monomer is 3 - methyl - 5 - furylpyrazoline, it is preferred that the reaction temperature is 150 to 1600C, and that the number of parts by weightthereof is 1 to 3 per 5 parts by weight of epoxy resin.
The resulting powders have better storage life (up to 6 months without deterioration of the original properties) and blocking resistance (up to 45 days without clogging) than broadly similar powdered modified epoxy resins. The method according to the invention is technically simple and does not need complicated equipment. The desired modified epoxy resin can be obtained in high yield (that is, up to about 92%).
It is sometimes advantageous for the reaction to be carried out in the presence of trifuryl borate, perferably in an amount of 0.05 to 0.6 parts by weight per 5 parts by weight of epoxy resin. By this means powders which are self-extinguishing or noninflammable can be obtained.
The powdered modified epoxy resins prepared according to the invention can be cured in the normal way; the resulting cured polymers may have good heat deformation properties, such as a Vicat softening point of up to 230"C.
In orderthat the invention may be more fully understood, the following Examples are given by way of illustration only.
Example 1
Into a reactor provided with a heating means, reflux condenser, thermometer and a stirrer there were charged 700 g of an epoxy resin produced by polycondensation of epichlorohydrin and diphenylolpropane, the resin having 22 to 24% epoxy groups, and 28 g of furfuramide (the weight ratio between these components was 5:0.2).
The reactor was heated to 16000 and the components were allowed to react at this temperature for 12 hours. The resulting furan-epoxy binder (obtained in a yield of 92%) was discharged from the reactor, cooled to 200C and ground to a powder of predetermined particle size.
Example 2.
Into a reactor similar to that described in Example 1, there was charged 700g of an epoxy resin having 20 to 22% epoxy groups which was produced from epichlorhydrin and diphenylol propane, and 140 g of fu rfu ramide. The weight ratio between these components was 5:1.
The reactor was heated to 145"C and the components were allowed to react at this temperature for 1.3 hours. The resulting furan-epoxy binder (obtained in a yield of 90%) was discharged from the reactor, cooled to 25"C and then ground to a powder.
Example 3.
Into a reactor as described in Example 1 there were charged 700 g of an epoxy resin produced from diphenylolpropane and epichlorhydrin, the resin having 18 to 20% epoxy groups, and 350 g offur- furamide (the weight ratio between these components was 5:2.5).
The components were allowed to react at 145"C for 1.2 hours. The resulting furan-epoxy binder (obtained in a yield of 88%) was discharged from the reactor, cooled to 30"C and ground to a powder.
Example 4.
Into a reactor as described in Example 1 there were charged 700 g of an epoxy resin produced from diphenylolpropane and epichlorhydrin, the resin having 16 to 18% groups, and 450 g of fu rfuramide (the weight ratio between these components being 5:3.2).
The components were allowed to react at 140 C for 1.2 hours. The resulting furan-epoxy binder (obtained in a yield of 88%) was discharged from the reactor, cooled to 25"C and ground to a powder.
Example 5.
Into a reactor as described in Example 1 there were charged 700 g of an epoxy resin produced from diphenylolpropane and epichlorhydrin, the resin having 14to 16% epoxy groups, and476goffur- furamide (the weight ratio between these components being 5:3.4).
The components were allowed to react at 1400C for one hour. The resulting product (obtained in a yield of 90%) was discharged from the reactor, cooled to 150"C and ground to a powder.
Example 6
Into a reactor as described in Example 1 there were charged 700 g of an epoxy resin as used in
Example 1 and 289 of 3 - methyl - 5 - furylpyrazoline (the weight ratio between these components being 5:0.2).
The components were allowed to react at 160 C for 1.5 hours. The resulting product (obtained in a yield of 92%) was discharged from the reactor, cooled to 20"C and ground to a powder.
Example 7.
Into a reactor as described in Example 1 there were charged 700 g of an epoxy resin as used in
Example 2 and 140 g of 3 - methyl - 5 - furyl pyrazoline (the weight ratio between these components being 5:1).
The components were allowed to react at 160"C for 1.5 hours. The resulting product (obtained in a yield of 90%) was discharged from the reactor, cooled to 25"C and disintegrated to form a powder.
Examples Into a reactor as described in Example 1 there were charged 700 g of an epoxy resin as used in
Example 3 and 350 g of 3 - methyl - 5 - furyl
pyrazoline (the weight ratio between these compo
nents being 5:2.5).
The components were allowed to react at 155"C for
1.3 hours. The resulting product (obtained in a yield
of 88%) was discharged from the reactor, cooled to
the temperature of 30"C and disintegrated to a
powder-like condition.
Example 9
Into a reactor as described in Example 1 there
were charged 700 g of an epoxy resin as used in
Example 4 and 420 g of 3 - methyl - 5 - furyl
pyrazoline (the weight ratio between these compo
nents being 5:3).
The components were allowed to react at 150"C for
1.5 hours. The resulting product (obtained in a yield of 90 /O) was discharged from the reactor and disintegrated, after cooling to 15"C, to form a powder.
Example 10
Into a reactor as described in Example 1, there were charged 700 g of an epoxy resin as used in
Example 5 and 450 g of 3 - methyl - 5 - furylpyrazoline (the weight ratio between these components being 5:3.2).
The components were allowed to react at 145"C for
1.2 hours. The resulting producted (obtained in a yield of 92%) was discharged from the reactor cooled two?000 and disintegrated to form a powder.
Example 11
Into a reactor as described in Example 1 there were charged 700 g of an epoxy resin as used in
Example 3 and 476 g of 3 - methyl - 5 - furylpyrazoline (the weight ratio between these compo
nents being 5:3.4).
The components were allowed to react at 1400C fqr one hour. The resulting product (obtained in a yield
of 90%) was discharged from the reactor, cooled to 20"C and disintegrated to form a powder.
Example 12
Example 1 was repeated, except that to the initial components there were added 7 g of trifurylborate (the weight ratio between trifurylborate and the epoxy resin being 0.05:5). The yield of the resulting product was 92%.
Example 13
Example 2, was repeated, except that the initial components there were added 28 g oftrifurylborate (the weight ratio between trifurylborate and the epoxy resin being 0.2:5). The yield of the resulting product was 91%.
Example 14
Example 3 was repeated, except that to the initial components there were added 42 g oftrifurylborate (the weight ratio between trifurylborate and the epoxy resin being 0.3:5). The yield of the resulting product was 89%.
Example 15.
Example 6 was repeated, except that to the initial components there were added 7 g of trifurylborate (the weight ratio between trifurylborate and the epoxy resin being 0.05:5). The yield of the resulting product was 92%.
Example 16
Example 7 was repeated, except that to the initial components there were added 28 g of trifurylborate
(the weight ratio between trifurylborate and the epoxy resin being 0.2:5). The yield of the resulting product was 90%.
Example 17
Example 8 was repeated, except that to the initial components there were added 42 g of trifurylborate (the weight ratio between trifurylborate and the epoxy resin being 0.3:5). The yield of the resulting product was 89%.
Example 18
Example 4 was repeated, except that to the initial components there were added 70 g of trifurylborate (the weight ratio between trifurylborate and the epoxy resin being 0.5:5). The yield of the resulting product was 88%.
Example 19
Example 5 was repeated, except that to the initial components there were added 84 g of trifurylborate (the weight ratio between trifurylborate and the epoxy resin being 0.6:5). The yield of the resulting product was 90%.
Example 20
Example 10 was repeated, except that to the initial components there were added 70 g of trifurylborate (the weight ratio between trifurylborate and the epoxy resin being 0.5:5). The yield of the resulting product was 92%.
Example 21 Example 11 was repeated, except that to the initial components there were added 84 g of trifurylborate (the weight ratio between trifurylborate and the epoxy resin being 0.6:5). The yield of the resulting product was 90%.
Comparative Example 1
Into a reactor as described in Example 1 there were charged 1009 of an epoxy resin produced from diphenylolpropane and epichlorhydrin, 100g of difurfurylidine acetone and 1009 offurfuramide.
The reactor was heated to 1400C and the components were allowed to react at this temperature; the resulting product was cooled to 30"C and ground to a powder.
In the following Table 1 there are shown the properties of furan-epoxy powders produced according to the above-mentioned Examples 1 to 21 and Comparative Example 1.
The powders produced according to Examples 1 to 21 were cured at a temperature of from 120 to 200"C with a pause of 6 hours after each 20"C. The cured polymers produced from the powders of Examples 1 to 11 were inflammable, those produced from the powders of Examples 12 to 17 were selfextinguishing and those produced from the powders of Examples 18 to 21 were non-inflammable. All the cured polymers were resistant to acids and alkalies.
Other properties of the cured polymers are given in the following Table 2.
Acetone Epoxy Storage Days
Example Appearance M.p. Ubbelohde solu- group Life to
No. of powder ( C) drop point bility content months blocking
1 Light 85 109 Total 4.5 6 35
brown to
dark
brown
2 ,, 83 107 ,, 2.8 6 40
3 ,, 88 118 ,, 2.6 6 40
4 ,, 82 104 ,, 2.0 6 45
5 " 90 120 ,, 1.7 6 35
6 ,, 78 98 ,, 4.3 6 40
7 ,, 86 102 ,, 3.2 6 45
8 ,, 92 114 ,, 2.9 6 45
9 " 88 110 ,, 2.3 6 45 10 ,, 76 106 ,, 2.0 6 40 11 " 75 103 " 1.8 6 35 12 ,, 86 111 ,, 4.1 6 40 13 " 83 108 ,, 3.7 6 40 14 ,, 87 115 ,, 2.8 6 45 15 ,, 84 108 ,, 4.0 6 40 16 ,, 90 120 ,, 3.2 6 45 17 ,, 79 110 ,, 2.5 6 35 18 " 85 108 " 2.3 6 40 19 " 91 123 ,, 1.8 6 40 20 ,, 87 105 ,, 2.6 6 40 21 " 75 102 ,, 1.9 6 45
Compara- Dark 92 114 ,, - 3 30 tive 1 brown
Table 2
Polymer of Polymer of
Examples 1 to 5, Examples 6 to 10
11to14,18 15to17
Property and 21 and 20
Vicat deformation heat- 130-230 202-230
resistance, C
Ultimate compression 900-1,500 950-1,650
strength, kgf/cm2
Ultimate strength upon 250-300 300-370
static bending, kgf/cm2
Brinnel hardness, kgf/cm2 1600-3000 2000-3500
Coke number, % 47-56 49-58
Dielectric loss angle at 50 Hz,
at the temperature of 20 C 27.10-3-30.10-3 28.10"3-32.10-3
Claims (7)
1. A method of preparing a powdered modified epoxy resin, which comprises reacting 5 parts by weight of an epoxy resin produced from diphenylol propane and epichlorhydrin with 0.2 to 3.4 parts by weight offurfuramide or 3 - methyl - 5 - fu rylpyrazoline at a reaction temperature of 140 to 1600C, followed by cooling to a temperature not exceeding 30 C and grinding to produce a powder.
2. A method according to claim 1 in which 5 parts by weight of the epoxy resin are reacted with 1 to 3 parts by weight offurfuramide or 3 - methyl - 5 furylpyrazoline.
3. A method according to claim 2, in which the reaction temperature is at ieast 150 C.
4. A method according to any of claims 1 to 3, in which the reaction is carried out in the presence of 0.05 to 0.6 parts by weight of trifurylborate.
5. A method of prpearing a powdered modified epoxy resin, substantially as herein described in any of Examples 1 to 21.
6. A powdered modified epoxy resin, when produced by a method according to any of claims 1 to 5.
7. A cured polymer produced by curing a powdered modified epoxy resin according to claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7901725A GB2039489B (en) | 1979-01-17 | 1979-01-17 | Powdered modified epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7901725A GB2039489B (en) | 1979-01-17 | 1979-01-17 | Powdered modified epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2039489A true GB2039489A (en) | 1980-08-13 |
| GB2039489B GB2039489B (en) | 1983-01-26 |
Family
ID=10502574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7901725A Expired GB2039489B (en) | 1979-01-17 | 1979-01-17 | Powdered modified epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2039489B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4109684A1 (en) * | 1990-07-25 | 1992-01-30 | Atg Electronic Gmbh | CONTACTING DEVICE FOR TEST PURPOSES |
-
1979
- 1979-01-17 GB GB7901725A patent/GB2039489B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4109684A1 (en) * | 1990-07-25 | 1992-01-30 | Atg Electronic Gmbh | CONTACTING DEVICE FOR TEST PURPOSES |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2039489B (en) | 1983-01-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |