GB2048908A - Unsaturated Polyester Resins Particularly Adapted for the Manufacture of Buttons - Google Patents
Unsaturated Polyester Resins Particularly Adapted for the Manufacture of Buttons Download PDFInfo
- Publication number
- GB2048908A GB2048908A GB8013897A GB8013897A GB2048908A GB 2048908 A GB2048908 A GB 2048908A GB 8013897 A GB8013897 A GB 8013897A GB 8013897 A GB8013897 A GB 8013897A GB 2048908 A GB2048908 A GB 2048908A
- Authority
- GB
- United Kingdom
- Prior art keywords
- fact
- buttons
- unsaturated polyester
- dimethylterephthalate
- alkyd
- 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.)
- Withdrawn
Links
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 16
- 229920000180 alkyd Polymers 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000001530 fumaric acid Substances 0.000 claims abstract description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004641 Diallyl-phthalate Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 7
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims abstract description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 239000011265 semifinished product Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 abstract description 3
- 229940117969 neopentyl glycol Drugs 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A process for the preparation of solid, non compactable unsaturated polyester resins comprises reacting, in a first stage, neopentylglycol or 1,4- butanediol or a mixture thereof, with dimethylterephthalate at 140- 190 DEG C, until the reaction is completed and in a second stage, the product thus obtained is reacted with fumaric acid or maleic anhydride in the presence of a solvent at about 200 DEG C until an acid number of preferably 12-13 is reached. The alkyd is milled and mixed with diallylphthalate and conventional accelerators and catalysts.
Description
SPECIFICATION
Unsaturated Polyester Resins, Particularly Adapted for the Manufacture of Buttons
The present invention relates to new unsatureted polyester resins, adapted for making products, in particular buttons, by hot moulding, as well as to process for the preparation of said resins. The present invention further relates to the products, in particular buttons, obtained from said unsaturated polyester resins. Further objects of the invention will be defined hereinafter.
An object of the present invention is therefore a process for the preparation of unsaturated polyester resins, which are solid and are not self-compacting, and which are particularly adapted for the production of manufacts, in particular buttons, characterized by the fact that it comprises mixing and alkyd, obtained by the reaction of
a) a glycol, -chosen among neopentylglycol, 1 ,4-butandediol or a mixture thereof, with
b) dimethylterephthalate and fumaric acid or maleic anhydride,
with diallylphthalate and conventional accelerators and catalysts, the preparation of the alkyd being effected in two distinct stages, in the first of which the aforesaid glycol is reacted with dimethylterephthalate at a temperature comprised between 1400 and 1900 C, until the reaction of the dimethylterephthalate has been completed, and subsequently, in a second stage, the product thus obtained is reacted with fumaric acid or maleic anhydride in the presence of a solvent at a temperature about 200"C until an acid number from 12 to 1 8, preferably from 12 to 13, is reached.
The completion of the transesterification of the dimethylterephthalate, in said first stage is evidenced by the end of the evolution of methyl alcohol.
According to the present invention, from 0.3 to 0.65 mols of dimethylterephthalate and 0.35 to 0.7 mols of fumaric acid or maleic an hydride are employed for each mol of glycol.
At the end of the polyesterification it is necessary to eliminate the solvent, e.g. by introduction with an inert gas or by application of a vacuum.
During the preparation of the alkyd, the oligomers and the low condensates are suitably eliminated from the reaction space when the acid number has attained values of about 33-45 by the introduction of large amounts of inert gas into the reactor or by applying a vacuum.
According to the present invention, it is further convenient to subject the alkyd, after cooling to room temperature, to fragmentation and milling before adding the diallyphthalate and the other conventional additives, which are necessary for the cross-linking- and the moulding of the resin.
Conveniently the fragmentation is effected in a crusher and the milling in a mill. The amount of diallylphthalate is suitably maintained, according to the invention, between 3 and 10, preferably between 4 and 7% by weight of the total of the-mixture.
A further object of the present invention are the unsaturated polyester resins obtained by the process hereinbefore described.
The unsaturated polyester resins, according to the present invention, are solid and are particularly adapted, after addition of a suitable agent for facilitating removal from the mould and possibly of dyestuffs, for making products by hot moulding under pressure.
A further object of the present invention are therefore the products, in particular the buttons, obtained from the polyester resins hereinbefore mentioned, as well as a process for their production.
Said process is characterized by the face that the mixture which contains said polyester, a conventional mould release agent, and optionally dyestuffs, is melted preferably at a temperature between 100 and 1 200C and the melt thus obtained is discharged in the desired form (e.g. in the form of a cylinder) and is then cooled and finally cut up-to obtain a blank (disk) which is hot moulded in suitable moulds for obtaining semi-finished products.
The peculiarity of the disks is that when they are massed the ones on the others in containers, at room temperature, they do not become deformed and do not adhere the ones to the other, viz. are not self-compacting.
From said-finished products, which form a further object of the present invention, finished products, e.g. buttons, are obtained by the techniques which are conventional in the ureic resin button art.
The buttons obtained from the semi-finished products according to the present invention, have the following advantages with respect to those obtained from ureic resins:
no need to open the moulds for degassing;
markedly superior transparency and gloss;
greater resiliency (resistance to shock);
greater resistance to chemical agents;
better workability, in particular a turning speed which practically doubled;
less scraps due to breakages during mechanical working.
The buttons obtained from the resins according to the present invention have the advantage, with respect to those obtained by centrifugation from conventional polyester resins, that there is absolutely no scrap (the manufacture of buttons from conventional polyester resins produces about 30% of scrap), and that they have a better appearance than those made by any other systems.
The following examples are illustrative and are not intended to limit the scope of the invention.
Example 1
Preparation of a Solid, Non Self-compacting Alkyd 1 550 kg of neopentylglycol
355 kg of 1,4-butanediol 21 64 kg of dimethylterephthalate
1.8 kg of stannous oxalate
0.8 kg of lithium hydroxide are introduced into a stainless steel AISI 316 industrial reactor having a capacity of 5000 liters, provided with a port for introducing the reagents, a mechanical paddle stirrer provided with an antideflagrant electrical motor, condenser, steam heating jacket, and discharge for the products.
While the mixture is stirred and a nitrogen stream is passed through, the temperature is brought to 1 700C. After two hours at said temperature, 70 liters of xylene (mixture ofthe three isomers) are added and the temperature is raised to 1 800C and then to 2000 C.
Once the distillation of the methanol has ceased, 860 kg of fumaric acid and 120 liters of the same xylene previously used, are added, taking care that the xylene entrained with the nitrogen stream is condensed and refluxed into the reactor. When the acid value has reached about 45 (mg of KOH per g of alkyd) as much nitrogen is introduced, without refluxing the xylene, as-needed to reach an acid number of 1 6-1 8. At this point the reaction mass is cooled and discharged into drums, in which the alkyd solidifies. The materials crushed and is milled in a mill until a grain size varying between 1 micron and 2 mm is obtained.
Example 2
Preparation of Round Button Blanks from the Alkyd Described in Example 1
From the milled alkyd obtained according to Example 1, a mixture is prepared having the following composition:
Alkyd of Example 1 90.6 parts by weight Diallylphthalate 5 parts by weight
Zinc stearate 2.5 parts by weight
Magnesium oxide 0.6 parts by weight
Tertiary butylperbenzoate 1.1 parts by weight
Pigment 0.02 parts by weight
Said mixture is melted, homogenized and extruded in the form of a bar. The bar is cut into sections of suitable thicknesses and cooled, whereby blanks (disks) are obtained.
The disks are placed in a mould in the hot, under pressure, to impart to them the desired form of a button, and are polymerized within 1.5-2.5 minutes, depending on the mould temperature, which may vary from 160 to 1900C.
Claims (13)
1. Process for the preparation of unsaturated polyester resins, which are solid and non selfcompacting, and which are particularly adapted for making products, in particular buttons, characterized by the fact that it comprises mixing and alkyd, obtained by the reaction of
a) a glycol, chosen among neopentyiglycol, 1-,4-butanediol or a mixture thereof, with
b) dimethylterephthalate and fumaric acid or maleic anhydride, with diallylphthalate and conventional accelerators and catalysts, the preparation of the alkyd being effected in two distinct stages, in the first of which the aforesaid glycol is reacted with dimethylterephthalate at a temperature comprised between 1400 and. 1 900C, until the reaction of the dimethylterephthalate has been completed, and subsequently, in a second stage, the product thus obtained is reacted with fumaric acid or maleic anhydride in the presence of a solvent at a temperature about 2000C until an acid number from 12 to 18, preferably from 12 to 13, has been reached.
2. Process according to Claim 1, characterized by the fact that 0.3 to 0.65 mols of dimethylterephthalate and 0.35 to 0.7 mols of fumaric acid or maleic anhydride are employed for each mol of glycol.
3. Process according to at least one of Claims 1 or 2, characterized by the fact that the oligomers and low condensates are eliminated from the reaction space, by introduction of large amounts of an inert gas into the reactor or by application of vacuum, when the acid number has reached values about 35-45.
4. Process according to at least one of Claims 1 to 3, characterized by the fact that the. alkyd obtained is subjected, after cooling to room temperature, to a milling before the diallylphthalate and the other conventional additives, required for the cross-linking and the moulding of the resin, are added.
5. Pyocess according to at least one of the preceding claims, characterized by the fact that an amount of diallylphthalate comprised between 3 and 10%, preferably 4 and 7%, by weight of the total of the mixture, is employed.
6. Unsaturated polyester resins, characterized by the fact that they have been obtained by the process according to Claims 1 to 5.
7. Process for the production of semi-finished manufacturers characterized by the fact that an unsaturated polyester resin according to the preceding claims is mixed with a conventional mould release agent and optionally dye stuffs, the mixture thus obtained is melted, the melt thus obtained is discharged in the desired form (for example a cylinder), is cooled and is finally cut to obtain a blank (disk) which is hot moulded in suitable moulds.
8. Semi-finished products, characterized by the fact that they have been obtained by the process of Claim 7.
9. Process for the production of buttons, characterized by the fact that they have been produced from the semi-finished products of Claim 8, by moulding techniques similar to those used to mould ureic resin buttons.
10. Buttons characterized by the fact that they have been produced by the process of Claim 9.
11. Process for the preparation of unsaturated polyester resin, substantially as herein described with reference to Example 1.
i 2. Process for the production of buttons, substantially as herein described with reference to
Example 2.
13. The features as herein disclosed, or their equivalents in any novel selection.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT22435/79A IT1113360B (en) | 1979-05-08 | 1979-05-08 | UNSATURE POLYESTER RESINS, PARTICULARLY SUITABLE FOR THE PRODUCTION OF BUTTONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2048908A true GB2048908A (en) | 1980-12-17 |
Family
ID=11196271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8013897A Withdrawn GB2048908A (en) | 1979-05-08 | 1980-04-28 | Unsaturated Polyester Resins Particularly Adapted for the Manufacture of Buttons |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE3016332A1 (en) |
| FR (1) | FR2456119A1 (en) |
| GB (1) | GB2048908A (en) |
| IT (1) | IT1113360B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262510A (en) * | 2022-01-17 | 2022-04-01 | 浙江飞素服饰有限公司 | Environment-friendly grain resin button and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1720406A1 (en) * | 1967-08-03 | 1971-06-16 | Hoechst Ag | Process for the production of unsaturated polyester resins |
-
1979
- 1979-05-08 IT IT22435/79A patent/IT1113360B/en active
-
1980
- 1980-04-28 DE DE19803016332 patent/DE3016332A1/en not_active Withdrawn
- 1980-04-28 GB GB8013897A patent/GB2048908A/en not_active Withdrawn
- 1980-05-08 FR FR8010320A patent/FR2456119A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262510A (en) * | 2022-01-17 | 2022-04-01 | 浙江飞素服饰有限公司 | Environment-friendly grain resin button and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| IT7922435A0 (en) | 1979-05-08 |
| FR2456119A1 (en) | 1980-12-05 |
| IT1113360B (en) | 1986-01-20 |
| DE3016332A1 (en) | 1980-11-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |