GB2181442A - Phenol-formaldehyde resin - Google Patents
Phenol-formaldehyde resin Download PDFInfo
- Publication number
- GB2181442A GB2181442A GB08620861A GB8620861A GB2181442A GB 2181442 A GB2181442 A GB 2181442A GB 08620861 A GB08620861 A GB 08620861A GB 8620861 A GB8620861 A GB 8620861A GB 2181442 A GB2181442 A GB 2181442A
- Authority
- GB
- United Kingdom
- Prior art keywords
- phenol
- formaldehyde
- temperature
- reaction
- reactants
- 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.)
- Granted
Links
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 87
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 8
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011491 glass wool Substances 0.000 claims description 10
- 239000011490 mineral wool Substances 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007859 condensation product Substances 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229960004279 formaldehyde Drugs 0.000 claims 10
- 230000001419 dependent effect Effects 0.000 claims 1
- 239000002244 precipitate Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- 238000001556 precipitation Methods 0.000 description 7
- 235000012255 calcium oxide Nutrition 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- -1 gysum Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
In a process for the production of an aqueous solution of a thermosetting phenol-formaldehyde resin, after phenol and formaldehyde have been reacted in the presence of a catalyst containing calcium, the pH of the product is adjusted by means of hydrofluoric acid or an ammonium salt thereof, which has been found to avoid the creation of a precipitate.
Description
SPECIFICATION
Improvements in or relating to phenol-formaldehyde resin
The present invention relates to phenol-formaldehyde resin and more particularly relates to a dilutable aqueous solution of a thermosetting phenol-formaldehyde resin with a low content of free unreacted phenol and relates to a process for the production of such a resin.
Varius methods have been proposed previously for the production of a phenol-formaldehyde resin having a low content of free unreacted phenol. In a typical prior process of this type a catalyst containing calcium is utilised, such as calcium oxide or calcium hydroxide. However, these prior methods have been found to be unsatisfactory on a commercial level, since frequently precipiations of calcium salts such as gysum, calcium phosphate or calcium carbonate are created during the addition of acid to the resin to effect the necessary pH-adjustment. Precipitations of this type have been generated with most of the acids that have been used so far.
Certain acids, however, such as hydrochloric acid, do not lead to a precipitate being generated, but instead suffer from other serious disadvantages. For example, if hydrochloric acid is utilised a hygroscopic calcium chloride salt is formed which is effectively impregnated in the resin. This leads to corrosion problems being experienced by the resultant resin. Also, if resins which include such calcium chloride salts are used in the manufacture of mineral wool products or glass wool products, the resultant products only have relatively poor thermal insulating properties.
The precipitation of salt as a consequence of the addition of acid to the resin to effect the necessary pH-adjustment also leads to problems in connection with the use of the resin. For example if the resin is to be utilised in the production of mineral wool products or glass wool products, any salt precipitate present in the resin may settle whilst the resin is stored in a storage tank, and the precipitate may also cause blockages in conduits and spray nozzles.
It is to be understood that there is a strong requirement, particularly from the environmental point of view, to be able to produce a phenol-formaldehyde resin which only has a low content of free phenol. Such a resin may be used, for example, in the manufacture of mineral wool products and glass wool products. However, at the present time it is regarded as impossible to manufacture, in a commercially acceptable manner, such a resin having a low content of free phenol, due to the precipitation problems outlined above.
The present invention seeks to reduce or obviate the disadvantages of the prior art as described above.
According to one aspect of this invention there is provided a process for the production of an aqueous solution of a thermosetting phenol-formaldehyde resin with a low content of free unreacted phenol, such process comprising the steps of mixing reactants comprising phenol and formaldehyde in an aqueous solution in the presence of a catalyst containing calcium and permitting the phenol and formaldehyde to react to form a phenol-formaldehyde resin, and finally adjusting the pH of the product by means of hydrofluoric acid or an ammonium salt thereof.
When the phenol and formaldehyde are mixed in the presence of the catalyst, an exothermic reaction takes place as the phenol and formaldehyde react to form a phenol-formaldehyde resin.
Preferably the phenol is mixed with a formaldehyde in an aqueous solution in the ratio of 2.1-4.5 moles of formaldehyde per mole of phenol.
Conveniently the catalyst is calcium oxide or calcium hydroxide and advantageously the catalyst is present in an amount of 3.5 to 7 per cent by weight of calcium calculated on the weight of the phenol.
In a preferred embodiment of the invention the exothermic increase of temperature of the mixture of phenol and formaldehyde is controlled so that the temperature of the reactants do not increase to more than about 52"C, at least during the first hour of the reaction. Conveniently the initial temperature is maintained in a range of 30-52"C, preferably in a range of 40-52"C.
Conveniently after the initial period of time during which the temperature of the reactants is regulated to be less than about 52"C, the reaction is allowed to continue, without the supply of heat, and the temperature of the reactants is permitted to rise up to a temperature of not more than about 68"C. Preferably, during this further reaction period, the temperature of the reactants is maintained in a range of 30-68"C, preferably 50-68"C, most preferably 60-68"C.
Advantageously, the process includes the penultimate step of cooling the condensation product of the phenol and the formaldehyde, after the phenol and formaldehyde have reacted completely to produce a condensation product substantially free from phenol but which is still soluble in water.
Preferably when the pH of the product is adjusted, the pH of the product is adjusted to a value of about 7-8.
In one process in accordance with the invention the phenol and calcium containing catalyst are initially mixed in water and subsequently the formaldehyde is added continuously to the mixture of phenol and catalyst to initiate the said reaction, but in alternative embodiments of the invention phenol, calciumcontaining catalyst and formaldehyde may all be mixed together simultaneously, or the formaldehyde and phenol are first mixed, and the calcium-containing catalyst is subsequently added to the mixture of formaldehyde and phenol.
Preferably the total reaction time for the steps of mixing the phenol and formaldehyde, conducting the exothermic reaction while maintaining the temperature, and continuing the reaction whilst permitting the reaction to proceed at an increase temperature has a total duration of between 4 and 36 hours, but advantageously said duration is in the region of 4-15 hours and most preferably in the region of 4-10 hours.
The invention also relates to an aqueous solution of a thermosetting phenol-formaldehyde resin having an unreacted phenol content of 0.05 per cent by weight or less, whenever made by a process as described above. The invention also relates to the use of such a thermosetting phenol-formaldehyde resin in the manufactue of glass wool or mineral wool.
It has been found that by utilising a preferred process in accordance with the invention a phenol-formaldehyde resin having a content of free unreacted phenol of between 0 and 0.5 per cent by weight can be produced.
Often the content of free unreacted phenol will be as low as 0 to 0.3 per cent by weight.
The invention will be explained further, by way of example, with reference to the embodiment examples given below, of which
Examples 1, 2 and 6 illustrate the manufacture of phenol-formaldehyde resin in accordance with the invention, whilst Examples 3, 4 and 5 relate to comparison tests outside the scope of the invention.
Example 1
125 g water and 600 g phenol were charged into a 2 litre glass vessel, 38 g calcium oxide (quick lime with 96.5% active content of CaO) was added while stirring. Then 1340 g formaldehyde-water solution containing 50 per cent by weight formaldehyde was added gradually over a period of about 30 minutes while stirring.
The molar ratio of phenol to formaldehyde in the mixture was 1:3.5. The amount of the calcium oxide catalyst was 4.4 per cent by weight calculated as calcium on the weight of the phenol.
The glass vessel was cooled the whole time so that the temperature did not exceed 50"C.
After about 1 hour the temperature was allowed to increase to 65"C. The temperature was kept at this value for 4 hours, and at the end of this time the content of free formaldehyde of the resin composition had been reduced to 8 per cent by weight. Then the composition was cooled to 25"C. The product then had a pH of 8.6.
The content of free phenol in the resin obtained was 0.3 per cent by weight.
The resin was neutralized with hydrofluoric acid to a pH of 7.5. No precipitation or thixotropy could be noticed in the neutralized resin.
No precipitation or thixotropy arose after the resin was stored for 4 months at a temperature of about 8"C. There was no problem when the resin was subsequently used as a binder for mineral wool or glass wool.
Example 2
The process according to Example 1 was repeated with the difference that ammonium hydrogen fluoride was used for neutralization to pH 7.5 instead of hydrofluoric acid. The same good result as according to Example 1 was obtained.
Example 3
The process according to Example 1 was repeated with the difference that the resin was neutralised with diluted sulphuric acid to pH 7.5. A whitish, fine-grained precipitate of gypsum was obtained, which little by little settled to the bottom. Because of the precipitate the resin could not be used as a binder for glass wool and mineral wool.
Example 4
The process according to Example 1 was repeated with the difference that the resin was neutralized with phosphoric acid to pH 7.5. Calcium phosphate was formed and the resin consequently became very thixotropic, so that the resin could not be poured any more. Therefore, the resin could not be used as a binder for glass wool and mineral wool.
Example 5
The process according to Example 1 was repeated with the difference that the resin was neutralised with carbonic acid to pH 7.5.
A whitish precipitate of calcium carbonate was formed. It slowly settled to the bottom. Due to the precipitate the resin could not be used as a binder for glass wool and mineral wool.
Example 6
125 g water, 600 g phenol and 1340 g formaldehyde water solution containing 50 per cent by weight formaldehyde were charged, with stirring, into a 2 litre glass vessel. While stirring and cooling 53.5 g calcium hydroxide (90.5 per cent by weight active content of
Ca(OH)2) was added gradually to the vessel.
The molar ratio of phenol to formaldehyde in the mixture was 1:3.5. The amount of the calcium hydroxide catalyst was 4.4 per cent by weight calculated as calcium on the weight of the phenol.
The temperature of the mixture was controlled so that it did not exceed 50"C. After about 1 hour the temperature was allowed to increase to 65"C. The temperature was kept at said value for 5 hours. The content of free formaldehyde of the resin composition was thus reduced to 8 per cent by weight. Then the composition was cooled to 25"C. The resin then had a pH of 8.5 and the content of free phenol was 0.3 per cent by weight.
The resin was neutralized with hydrofluoric acid to pH 7.5. No precipitation or thixotropy could be noticed in the neutralized resin. No precipitation or thixotropy arose after storage of the resin for 4 months at about 8"C. There were no problems during the subsequent use of the resin as a binder for mineral wool or glass wool.
The invention is not limited to the embodiments shown, since these can be modified in different ways within the scope of the invention.
Claims (25)
1. A process for the production of an aqueous solution of a thermosetting phenolformaldehyde resin with a low content of free unreacted phenol, such process comprising the steps of mixing reactants comprising phenol and formaldehyde in an aqueous solution in the presence of a catalyst containing calcium and permitting the phenol and formaldehyde to react to form a phenol-formaldehyde resin, and finally adjusting the pH of the product by means of hydrofluoric acid or an ammonium salt thereof.
2. A process according to claim 1, wherein the phenol is mixed with a formaldehyde in an aqueous solution in the ratio of 2.1-4.5 moles of formaldehyde per mole of phenol.
3. A process according to claim 1 or claim 2, wherein said catalyst is calcium oxide or calcium hydroxide.
4. A process according to claim 3, wherein the catalyst is present in an amount of 3.5 to 7 per cent by weight of calcium calculated on the weight of the phenol.
5. A process according to any one of the preceding claims, wherein the exothermic increase of temperature of the mixture of phenol and formaldehyde is controlled so that the temperature of the reactants do not increase to more than about 52"C, at least during the first hour of the reaction.
6. A process according to claim 5, wherein the temperature of the reactants is maintained in-a range of 30-52"C at least during the first hour of the reaction.
7. A process according to claim 5, wherein the temperature of the reactants is maintained in a range of 40-52"C at least during the first hour of the reaction.
8. A method according to claim 5, 6 or 7, wherein after the initial period of time during which the temperature of the reactants is regulated to be less than about 52"C, the reaction is allowed to continue, without the supply of heat, and the temperature of the reactants is permitted to rise up to a temperature of not more than about 68"C.
9. A method according to claim 8, wherein when the reaction is allowed to continue the temperature of the reactants is maintained in a range of 30 to 68"C.
10. A method according to claim 8, wherein when the reaction is allowed to continue the temperature of the reactants is maintained in a range of 50-68"C.
11. A method according to claim 8, wherein when the reaction is allowed to continue the temperature of the reactants is maintained in a range of 60-68"C.
12. A process according to any one of the preceding claims, wherein the process includes the penultimate step of cooling the condensation product of the phenol and the formaldehyde, after the phenol and formaldehyde have reacted completely to produce a condensation product substantially free from phenol but which is still soluble in water.
13. A process according to any one of the preceding claims wherein when the pH of the product is adjusted, the pH of the product is adjusted to a value of about 7-8.
14. A method according to any one of the preceding claims wherein the phenol and calcium containing catalyst are initially mixed in water and subsequently the formaldehyde is added continuously to the mixture of phenol and catalyst to initiate the said reaction.
15. A method according to any one of claims 1 to 13, wherein the phenol, calciumcontaining catalyst and formaldehyde are all mixed together simultaneously.
16. A method according to any one of claims 1 to 13, wherein the formaldehyde and phenol are first mixed, and the calcium-containing catalyst is subsequently added to the mixture of formaldehyde and phenol.
17. A method according to claim 8 or any claim dependent thereof, the total reaction time for the steps of mixing the phenol and formaldehyde, conducting the exothermic reaction while maintaining the temperature, and continuing the reaction whilst permitting the reaction to proceed at an increase temperature has a total duration of between 4 and 36 hours.
18. A method according to claim 17, wherein the said total duration is in the region of 4-15 hours.
19. A method according to claim 17, wherin the said total duration is in the region of 4-10 hours.
20. A process substantially as herein described with reference to Example 1.
21. A process substantially as herein described with reference to Example 2.
22. A process substantially as herein described with reference to Example 6.
23. An aqueous solution of a thermosetting phenol-formaldehyde resin having an unreacted phenol content of 0.05 per cent by weight or less, whenever made by a process according to any one of the preceding claims.
24. The use of a thermosetting phenol-for maldehyde resin according to claim 23, in the manufacture of glass wool or mineral wool.
25. Any novel feature or combination of features disclosed herein.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8504038A SE445834B (en) | 1985-08-30 | 1985-08-30 | A WATER DISPOSAL OF A HARDENABLE PHENOL FORMAL HEADLINE WITH ADDED FREE PHENOL CONTENT AND PROCEDURE FOR PREPARING ITS SAME |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8620861D0 GB8620861D0 (en) | 1986-10-08 |
| GB2181442A true GB2181442A (en) | 1987-04-23 |
| GB2181442B GB2181442B (en) | 1988-09-14 |
Family
ID=20361240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08620861A Expired GB2181442B (en) | 1985-08-30 | 1986-08-28 | Improvements in or relating to phenol-formaldehyde resin |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE3628863C2 (en) |
| FR (1) | FR2586691B1 (en) |
| GB (1) | GB2181442B (en) |
| SE (1) | SE445834B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987007560A1 (en) * | 1986-06-12 | 1987-12-17 | Priha Oy | Phenol-based resin for the production of laminates and process for the preparation of the resin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR852139A (en) * | 1938-04-26 | 1940-01-24 | Ver Chemische Fabriken Kreidl | Process for the preparation of artificial resins and products obtained by this process |
| GB590684A (en) * | 1944-10-12 | 1947-07-25 | Tootal Broadhurst Lee Co Ltd | Improvements in the production of phenolic condensation products and treatment of materials therewith |
| FR2336438A1 (en) * | 1975-12-26 | 1977-07-22 | Sapic | COMPOSITION OF SELF-SETTING MOLDING MATERIALS AND PROCESS FOR CURING A SOLID OR HOLLOW BODY, MADE FROM A COMPOSITION OF SELF-SETTING MOLDING MATERIALS |
| DE3330982A1 (en) * | 1983-08-27 | 1985-03-07 | Dynamit Nobel Ag, 5210 Troisdorf | METHOD FOR PRODUCING A PHENOLESOL RESIN |
-
1985
- 1985-08-30 SE SE8504038A patent/SE445834B/en not_active IP Right Cessation
-
1986
- 1986-08-26 DE DE19863628863 patent/DE3628863C2/en not_active Expired - Fee Related
- 1986-08-27 FR FR8612139A patent/FR2586691B1/en not_active Expired
- 1986-08-28 GB GB08620861A patent/GB2181442B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987007560A1 (en) * | 1986-06-12 | 1987-12-17 | Priha Oy | Phenol-based resin for the production of laminates and process for the preparation of the resin |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3628863A1 (en) | 1987-03-05 |
| SE8504038D0 (en) | 1985-08-30 |
| DE3628863C2 (en) | 1996-05-23 |
| FR2586691A1 (en) | 1987-03-06 |
| SE445834B (en) | 1986-07-21 |
| GB8620861D0 (en) | 1986-10-08 |
| FR2586691B1 (en) | 1989-01-06 |
| GB2181442B (en) | 1988-09-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19980828 |