GB2050387A - Process for producing coloured polymers - Google Patents
Process for producing coloured polymers Download PDFInfo
- Publication number
- GB2050387A GB2050387A GB7918232A GB7918232A GB2050387A GB 2050387 A GB2050387 A GB 2050387A GB 7918232 A GB7918232 A GB 7918232A GB 7918232 A GB7918232 A GB 7918232A GB 2050387 A GB2050387 A GB 2050387A
- Authority
- GB
- United Kingdom
- Prior art keywords
- temperature
- colour
- hours
- colourant
- coloured
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Coloured polymers are produced by polymerising a vinyl monomer in the presence of a radical polymerisation initiator and a colourant which is a sulphoxide, tributylphosphate, diisoamylphosphonate, trialkyl-, or triaryl phosphinoxide, or di-2- ethylhexylphosphoric acid complex of a coloured metal chloride or nitrate.
Description
SPECIFICATION
Process for producing coloured polymers
The present invention relates to the production of high-molecular weight substances, and more particularly to a process for producing coloured polymers.
Coloured polymers find extensive use in various industries such as aircraft engineering, car manufacture, civil engineering and the textile industry. The present invention provides a process for producing a coloured polymer. According to the invention, a vinyl monomer is polymerised in the presence of a radical-type initiator and a colourant, the colourant being a sulphoxide, tributylphosphate, diisoamylphosphonate, trialkyl/aryl/phosphinoxide or di-2-ethylhexylphosphoric acid complex of a metal chloride or metal nitrate.
The use of these colourants makes it possible to obtain uniformly coloured polymers, whose colour depends on the choice of metal salt taking part in the complex formation. It is possible to use coloured nitrates or chlorides of any metals capable of forming complexes with the above-mentioned organic ligands.
It is advisable to use the colourant in an amount of from 0.1 to 2.0% by weight. When added in an amount of below 0.1% by weight, the colour of the polymer is likely to be very pale. When added in an amount of about 2% by weight or above, the colourant may exert a plasticising effect on the polymer.
If it is desired to make a polymer for use as a colour filter, the preferred complexes are the sulphoxide complexes of bivalent cobalt chloride, bivalent nickel nitrate and trivalent chromium nitrate.
In the process of the invention, the colourant is dissolved in a monomeric mixture (vinyl monomer, initiator, regulator), which is then subjected to free radical polymerisation at an appropriate temperature depending on the initiator and monomer used. The colourant has no significant effect on the polymerisation kinetics, so no changes are required in conventional polymerisation techniques. Apart from their colour, the physico-chemical characteristics of the resulting polymers remain unchanged.
The colourant is a sulphoxide, tributylphosphate, diisoamylphosphonate, trialkyl/aryllphosphinoxide or di-2-ethylhexylphosphoric acid complex of a coloured metal chloride or metal nitrate. The complexes may be prepared by intensively stirring a mixture of an aqueous solution of a coloured metal chloride or metal nitrate and a solution of the organic ligand(s) in a solvent, such as benzene, at for example room temperature for the period of 0.5 hour, for example. After separation of the resulting mixture into two layers, the organic layer (the solution of complex in benzene) is separated, the solvent is removed under vacuum and the resulting colourant is then ready for use.
Coloured polymers produced by the process of the invention have been subjected to tests for heat- and light-resistance. Since the complexes form molecular solutions in the vinyl monomer and in the final polymer, the polymers have a high degree of colour uniformity.
Light-resistance of the colour has been evaluated spectrophotometrically by the variation of intensity of coloration after exposure to UV-light over 50 hours. No changes of the coloration intensity have been observed.
For example, polymethylmethacrylate containing as colourant a complex of bivalent cobalt with two molecules of diamylsulphoxide, has been exposed to the light of a quartz low-pressure lamp for 50 hours.
There were no changes in the coloration intensity. Under similar conditions, a polymer coloured with an organic dye widely used in the art, i.e. "anthraquinone blue", showed a reduction in colour intensity of a factor of 2 after 5 hours' exposure.
In the tests for heat-resistance, the coloured polymers were subjected to a temperature of 180"C for 6 hours. The coloration intensity did not change. Furthermore, there is observed an increased heat-resistance ofthe resulting polymers.
Thus, polymethylmethacrylate containing 2.0% by weight of complex [CoC122(CSH11)2SOI starts to decompose at 280"C, and the temperature of intensive decomposition is 350"C. Uncoloured polymethylmethacrylate starts to decompose at 240"C, and its temperature of intensive decomposition is 295"C.
Polymethylmethacrylate containing the organic dye, "anthraquinone blue", starts to decompose at 2380C and its intensive decomposition temperature is 290"C.
It should be noted, in particular, that when the process of the present invention is used to produce coloured polymeric "glass" (e.g. polymethylmethacrylate), the latter has excellent spectral characteristics defined by a narrow region of light absorption by the metal salts, which is of a great value in the manufacture of colour filters.
Other physico-mechanical characteristics of the dyed polymers produced in accordance with the present invention, remain unchanged owing to a minor amount of the dye incorporated in the polymer.
In order that the invention may be more fully understood, the following Examples are given by way of illustration only.
Example 1
A mixture of total weight 5 kg, consisting of 50 g of a diamylsulphoxide complex of bivalent cobalt chloride CoClf2 [(C5H11)2SO],2.5 g of benzoyl peroxide and the balance methylmethacrylate, is placed in a silicate glass mould and polymerised at the temperature of 60"C for 8 hours. Then a post-polymerisation treatment is conducted at a temperature of 1 200C for 6 hours, to give a transparent optically uniform organic "glass" having a blue colour.
The coloration of samples of the resulting polymethylmethacrylate (spectral characteristics) remains unchanged after heat-treatment (at a temperature of 180"C for 6 hours) and after UV-irradiation (lamp
IIPK-2M, distance to the sample 10 cm, temperature 200C, 50 hours). Decomposition of the coloured polymethylmethacrylate started at 285"C, and became intensive at 3300C.
Example 2
The procedure of Example 1 is repeated except that the complex used is of tributylphosphate with bivalent cobalt chloride, in an amount of 1% by weight.
There is obtained a transparent optically uniform organic "glass" having a blue colour.
The colour of samples of the resulting polymethylmethacrylate remains unchanged after heat-treatment (at the temperature of 180"C for 6 hours) and after UV-irradiation (lamp IIPK-2M, distance to the sample 10 cm, temperature 20"C, 50 hours). Decomposition of the coloured polymethylmethacrylate begins at 290"C, and becomes intensive at 320"C.
Example 3
The procedure of Example 1 is repeated except that the complex used is a diisoamylphosphonate complex of bivalent cobalt nitrate
in an amount of 1% by weight. Atransparent optically uniform organic "glass" is thus obtained which has a pink colour. The colour of samples of the resulting polymethylmethacrylate remains unchanged after heat4reatment (at a temperature of 1 80C for 6 hours) and after UV-irradiation (lamp llPK-2M, distance to the sample 10 cm, temperature 20"C, 50 hours). Decomposition of the dyed polymethylmethacrylate begins at 285"C, and is intensive at 325"C.
Example 4
The procedure of Example 1 is repeated except that the complex used is of triphenylphosphinoxide with bivalent cobalt nitrate Co(NO3)22 [(C6H6)3PO., in an amount of 1% by weight.
A transparent optically uniform organic "glass" with a pink colour is obtained.
The colour of samples of the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 180'C for 6 hours) and after UV-irradiation (lamp IIPK-2M, distance to the sample 10 cm, temperature 20"C, 50 hours). Decomposition of the dyed polymethylmethacrylate begins at 290 C, and becomes intensive at 330"C.
Example 5
The procedure of Example 1 is repeated except that there is used a di-2-ethylhexylphosphoric acid complex of bivalent cobalt nitrate
in an amount of 1% by weight.
Atransparent optically uniform organic "glass" with a pink colour is obtained. The colour of samples of the dyed polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 1800C for 6 hours) and UV-irradiation (lamp IIPK-2M, distance to the sample 10 cm, temperature 200C, 50 hours).
Decomposition begins at 280"C, and is intensive at 31 0 C.
Example 6
The procedure of Example 1 is repeated except that the colourant is a diamylsulphoxide complex of trivalent chromium nitrate Cr(NO3)33 [(CsH")2SO) in an amount of 1% by weight.
Atransparent optically uniform organic "glass" is obtained, having a green colour.
The colour of samples of the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 1 80"C for 6 hours) and after UV-irradiation (lamp IIPK-2M, the distance to the sample 10 cm, the temperature 20"C, 50 hours). Decomposition of the coloured polymethylmethacrylate begins at 260"C, and is intensive at 300"C.
Example 7
The procedure of Example 1 is repeated except that the colourant is a tributylphosphate complex of trivalent chromium chloride Cry133 [(C4Hg0)3PO], ,in an amount of 1% by weight.
Atransparent optically uniform organic "glass" with a green colour is thus obtained.
The colour of the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 180"for6 hours) and UV-irradiation (lamp IIPK-2M, the distance to the sample is 10 cm, temperature 200C, 50 hours). Decomposition of the coloured polymethylmethacrylate begins at 270 C, and is intensive at 310"C.
Example 8
The procedure of Example 1 is repeated, except that the colourant used is a dihexylsulphide complex of nickel nitrate Ni(NO3)22 [(C6H13)2SO] in an amount of 0.5 S by weight.
An optically uniform organic "glass" is thus obtained which is of a green colour.
The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat treatment (at a temperature of 1 800C for 6 hours) and after UV-irradiation (lamp IIPK-2M), the distance to the sample 10cm, temperature 20"C, 50 hours). Decomposition of the coloured polymethylmethacrylate begins at 280"C, and is intensive at 32q"C.
Example 9
A mixture, of total weight 1 kg, consisting of 10 g of a colourant, i.e. a complex of bivalent cobalt chloride with two molecules of diisoamylsulphoxide; 9 of benzoyl peroxide and the balance styrene, is placed under vacuum and polymerised in a silicate glass mould at a temperature of 60"C for 12 hours, and then post-polymerised for 5 hours at a temperature of 1300C, to give a uniformly coloured blue polystyrene.
The colour of samples of the resulting polystyrene remains unchanged after UV-irradiation (lamp IIPK-2M, the distance to the sample 20 cm, temperature 20"C, 30 hours). Decomposition of the dyed polystyrene starts at 300"C and becomes intensive at 350"C.
Example 10
The procedure of Example 9 is repeated except that as the colourant, use is madeof di-2-ethyl-hexylphosphoric acid complex of nickel chloride
in an amount of 0.3% by weight. There is obtained a uniformly coloured green polystyrene.
The colour of samples produced from the resulting polystyrene remains unchanged after UV-treatment (lamp IIPK-2M, the distance to the sample 20 cm, temperature 20"C, 30 hours). Decomposition of the dyed polystyrene starts at 290"C, and is intensive at 345"C.
Example 11
The procedure of Example 9 is repeated except that as the colourant, use is made of a dihexylsulphoxide complex of manganese chloride MnCI22 [(C6H13)2SO] in an amount of 1.5% by weight. There is obtained a uniformly coloured pink polystyrene.
The colour of samples produced from the resulting polystyrene remains unchanged after UV-irradiation (lamp IIPK-2M, the distance to the sample 30 cm, temperature 20"C, 30 hours). Decomposition of the dyed polystyrene starts at 295"C, and is intensive at 350"C.
Example 12
The procedure of Example 9 is repeated, except that as the colourant use is made of a dihexylsulphoxide complex of niobium chloride NbCI5 3 [(C6H13)2SO] in an amount of 0.2% by weight. There is obtained a uniformly-coloured yellow polystyrene.
The colour of samples produced from the resulting polystyrene remains unchanged after UV-irradiation (lamp IIPK-2M, the distance to the sample 20 cm, temperature 20"C, 30 hours). Decomposition of the dyed polystyrene starts at 300 C, and is intensive at 3500C.
Example 13
A mixture consisting of 30 g of acrylonitrile, 0.05% by weight of benzoyl peroxide, 2% by weight of a complex of cobalt chloride with two molecules of diamylsulphoxide CoCl22 [(CH11 )2SO) , is charged into an ampoule, placed under vacuum, sealed and polymerised at a temperature of 50"C for three hours. Then the ampoule is opened, the precipitated polyacrylonitrile is filtered-off, thoroughly washed on a filter with petroleum ether; reprecipitated from dimethylformamide into petroleum ether, and dried under a vacuum at a temperature of from 30 to 40"C to a constant weight. There is obtained a polyacrylonitrile powder having a bluish tint and a softening point of 135"C. Filaments drawn from a melt of this polymer have a blue colour.
Example 14
The procedure of Example 13 is repeated except that as the colourant use is made of a tributylphosphate complex of cobalt chloride CoC122 [(C4H9O) 3PO) in an amount of 0.2% by weight. There is obtained a polyacrylonitrile powder having a blue colour and a softening point of 145"C. Filaments drawn from a melt of this polymer are of a bluish colour.
Example 15 Polyacrylonitrile is produced by the method of Example 13, except that as the colourant use is made of a trioctylphosphinoxide complex of molybdenum chloride in an amount of 2% by weight. There is obtained a polyacrylonitrile powder having a green tint and a softening point at 1400C. Filaments drawn from a melt of this polyacrylonitrile have a green colour.
Example 16
Polyacrylonitrile is produced by the method of Example 13, except that as the colourant use is made of a dihexylsulphoxide complex of palladium chloride PdC122 [(C6H13)2SO] in an amount of 0.5% by weight.
There is obtained a polyacrylonitrile powder having a yellow tint and a softening point of 1 50 C. Filaments drawn from a melt of this polyacrylonitrile have a yellowish colour.
Example 17
A mixture, of total weight 1 kg, consisting of 10 g of colourant, i.e. a tributylphosphate complex of cobalt nitrate Co(NO3)22 [(C4Hg0)3PO], 0.1 g of dicyclohexyiperoxidecarbonate, the balance being vinyl acetate, is placed under vacuum and polymerised at a temperature of 40"C for three hours. The precipitated polyvinylacetate is filtered off, thoroughly washed on a filter with petroleum ether, reprecipitated from dimethylformamide into petroleum ether and dried under a vacuum at a temperature in the range 30 to 40"C, to a constant weight, to give a polyvinylacetate powder having a pink tint, and a softening temperature of 145"C.
Example 18
The procedure of Example 9 was repeated, except that the monomer is butyl acrylate and as the colourant use is made of a dihexylsulphoxide complex of molybdenum chloride MoC153 [(C6H13)2SO] in an amount of 2.0% by weight dissolved in the butylacrylate. There is obtained a uniformly-coloured green polybutylacrylate. The colour of samples produced from the resulting polybutylacrylate remains unchanged after
UV-irradiation (lamp IIPK-2M, the distance to the sample 20 cm, temperature 20"C, 30 hours). Decomposition of the coloured polybutylacrylate begins at 240"C, and is intensive at 3000C.
Example 19
The procedure of Example 1 is repeated except that as the colourant use is made of a triphenylphosphinoxide complex of uranyl nitrate (UO2) (NO3)2 2 [(C6H5)3PO] in an amount of 2% by weight. There is obtained a transparent optically-uniform organic "glass" having a yellowish-green colour. The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 1 800C for 6 hours) and after UV-irradiation (lamp IIPK-2M, the distance to the sample 10 cm, temperature 20"C, 50 hours). Decomposition of the coloured polymethylmethacrylate started at 285"C, and is intensive at 3300C.
Example 20
The procedure of Example 1 is repeated except that as the colourant use is made of a diamylsulphoxide complex of uranium chloride Us143 [(C5H1l)2SO] in an amount of 1.0% by weight. There is obtained a transparent optically uniform organic "glass" of a green colour.
The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 1 80"C for 6 hours) and after UV-irradiation (lamp llPK-2M, the distance to the sample 10 cm, temperature 20"C, 50 hours). Decomposition of the coloured polymethylmethacrylate begins at 290 C, and is intensive at 325"C.
Example 21
The procedure of Example 1 is repeated, except that as the colourant use is made of a tributylphosphate complex of selenium chloride SeCl42 [(C4H90)3PO] in an amount of 0.5% byweight. There is obtained a transparent optically uniform organic "glass" having a dark-brown colour.
The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 1800C for 6 hours) and after UV-irradiation (lamp IIPK-2M, the distance to the sample 10 cm, temperature 200C, 50 hours). Decomposition of the coloured polymethylmethacrylate starts at 2800C, and is intensive at 3200C.
Example 22
The procedure of Example 1 is repeated, except that as the colourant use is made of a di-2-ethylhexylphosphoric acid complex of molybdenum chloride MOC153 [HOP(O)(CH17)2] in an amount of 0.3% by weight. There is obtained a transparent optically uniform organic "glass" of a green colour.
The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 180"C for 6 hours) and after UV-irradiation (lamp IIPK-2M, the distance to the sample 10 cm, temperature 20"C, 50 hours). Decomposition of the coloured polymethylmethacrylate starts at 280"C, and is intensive at 320"C.
Example 23
The procedure of Example 1 is repeated, except that as the colourant use is made of a diamylsulphoxide complex of niobium nitrate Nb(NO3)33 [(CSH1l)2SO] in an amount of 2.0% by weight. There is obtained a transparent opticaily uniform organic "glass" having a blue colour.
The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 1 80"C for 6 hours) and after UV-irradiation (lamp IIPK-2M, the distance to the sample 10 cm, temperature 20 C, 50 hours). Decomposition of the coloured polymethylmethacrylate starts at 280"C, and is intensive at 320 C.
Example 24
The procedure of Example 1 is repeated, except that as the colourant use is made of a diamylsulphoxide complex of cerium nitrateCe(NO3)44 [(C5H11)2SO] in an amount of 2.0% by weight. There is obtained a transparent optically uniform organic "glass" having an orange colour.
The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 1 80"C for 6 hours) and after UV-irradiation (lamp 11 PK-2M, the distance to the sample 10cm, temperature of 20"C, 50 hours). Decomposition of the coloured polymethylmethacrylate starts at 285 C, and is intensive at 325 C.
Example 25
The procedure of Example 1 is repeated, except that as the colourant use is made of a cyclohexylsulphoxide complex of ferric nitrate Fe(NO3)33 [(C6H1o)SO ] in an amount of 0.1% by weight There is obtained a transparent optically uniform organic "glass" having a dark-brown colour.
The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 1800C for 6 hours) and after UV-irradiation (lamp IIPK-2M, the distance to the sample 10cm, temperature 20"C, 50 hours). Decomposition of the coloured polymethylmethacrylate starts at 250'C, and is intensive at 300 C.
Example 26
The procedure of Example 1 is repeated, except that as the colourant use is made of a cyclohexylsulphox ide complex of trivalent iron chloride FeCl33 [(C5H10)SO] in an amount of 0.1% by weight. There is obtained a transparent optically uniform organic "glass" having a brown colour.
The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 1 80"C for 6 hours) and after UV-irradiation (lamp IIPK-2M, the distance to the sample 10cm, temperature 200C, 50 hours). Decomposition of the coloured polymethylmethacrylate starts at 250"C, and is intensive at 300"C.
Example 27
The procedure of Example 1 is repeated, except that as the colourant use is made of a cyclohexylsulphoxide complex of vanadium chloride VC153 [(C6H10)SO] in an amount of 0.5% by weight. There is obtained a transparent optically uniform organic "glass" having a yellow-green colour.
The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 1 80 C for 6 hours) and after UV-irradiation (lamp 11 PK-2M, the distance to the sample 10 cm, temperature 20"C, 50 hours). Decomposition of the coloured polymethylmethacrylate starts at 250 C, and is intensive at 300 C.
Example 28
The procedure of Example 1 is repeated, except that as the colourant use is made of a diisoamylphosphonate complex of gold chloride
in an amount of 0.2% by weight. There is obtained a transparent optically uniform organic "glass" having an orange colour. The colour of samples produced from the resulting polymethylmethacrylate remains unchanged after heat-treatment (at a temperature of 180 C for 6 hours) and after UV-irradiation (lamp
IIPK-2M, the distance to the sample is 10 cm, temperature 200C, 50 hours). Decomposition of the coloured polymethylmethacrylate starts at 250"C, and is intensive at 305 C.
Claims (7)
1. A process for producing a coloured polymer which comprises polymerising a vinyl monomer in the presence of a radical-type initiator and a colourant which is a sulphoxide, tributylphosphate, diisoamylphosphonate, trialkyl aryliphosphinoxide or di-2.ethylhexylphosphoric acid complex of a coloured metal chloride or nitrate.
2. A process according to claim 1, wherein said colourant is used in an amount of from 0.1 to 2% by weight, based on the weight of monomer.
3. A process according to claim 1 or 2, wherein as the colourant a sulphoxide complex of bivalent cobalt is used.
4. A process according to claim 1 or 2, wherein a sulphoxide complex of bivalent nickel is used as the colourant.
5. A process according to claim 1 or 2, wherein a sulphoxide complex of trivalent chromium nitrate is used as the colourant.
6. A process for producing a coloured polymer substantially as herein described in any of the Examples.
7. A coloured polymer produced by the process of any preceding claim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7918232A GB2050387B (en) | 1979-05-24 | 1979-05-24 | Process for producing coloured polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7918232A GB2050387B (en) | 1979-05-24 | 1979-05-24 | Process for producing coloured polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2050387A true GB2050387A (en) | 1981-01-07 |
| GB2050387B GB2050387B (en) | 1983-05-18 |
Family
ID=10505436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7918232A Expired GB2050387B (en) | 1979-05-24 | 1979-05-24 | Process for producing coloured polymers |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2050387B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0175317A2 (en) * | 1984-09-18 | 1986-03-26 | BASF Aktiengesellschaft | Process for the manufacture of polymers containing carboxylic groups |
-
1979
- 1979-05-24 GB GB7918232A patent/GB2050387B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0175317A2 (en) * | 1984-09-18 | 1986-03-26 | BASF Aktiengesellschaft | Process for the manufacture of polymers containing carboxylic groups |
| EP0175317A3 (en) * | 1984-09-18 | 1987-01-28 | Basf Aktiengesellschaft | Process for the manufacture of polymers containing carboxylic groups |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2050387B (en) | 1983-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2846529C2 (en) | ||
| DE3382815T2 (en) | Energy polymerizable compositions containing organometallic initiators | |
| Grassie et al. | Thermal degradation of polymethacrylonitrile. Part V. The mechanism of the initiation step in coloration reactions | |
| Boston et al. | Phthalocyanine derivatives from 1, 2, 4, 5-tetracyanobenzene or pyromellitic dianhydride and metal salts | |
| US4150208A (en) | Method of polymerizing olefins | |
| CN110041712B (en) | Preparation method of thermoreversible color-changing composite material based on polydiacetylene and metal organic framework compound | |
| US4039467A (en) | Visibly opaque infrared transmitting optical filter containing a combination of copper and vanadyl phthalocyanine sulfonamides | |
| DE2802525A1 (en) | PROCESS FOR THE PRODUCTION OF CARBODIIMIDE-CONTAINING ORGANIC POLYISOCYANATE OR. A STABLE LIQUID FORM OF METHYLENE BIS (PHENYL ISOCYANATE) | |
| US3926835A (en) | Infrared transmitting filter containing 1,4,5,8-tetracyclohexylaminoanthraquinone | |
| US4259229A (en) | Process for producing colored polymer | |
| GB2050387A (en) | Process for producing coloured polymers | |
| DE69032420T2 (en) | Syndiotactic polymers of arylcyclobutene-functional monomers, process for their preparation and crosslinked derivatives made therefrom | |
| US3216958A (en) | Coloring thermoset resins with metalloorganic compounds | |
| DE3615765A1 (en) | POLYACETYLENE-BASED POLARISATORS AND THEIR PRODUCTION | |
| US4981886A (en) | Method for production of colored macromolecular polymer | |
| DE2908554A1 (en) | TWO-PHASE PIGMENT | |
| US3474039A (en) | Hard,machinable,transparent organopolysiloxane filters,their manufacture and use | |
| CN114716651A (en) | Alpha-vinyl bridged BODIPY conjugated polymer and preparation method thereof | |
| DE2920080C2 (en) | Process for the production of colored polymers | |
| Horvath et al. | Chromium (II) alkoxides | |
| Batty et al. | Polymerization of acrylonitrile in the presence of vinylsulphone dyes | |
| GB2116543A (en) | Metal complexes of halogen-substituted o-benzenedithiols, intermediates and processes therefor | |
| DE1569613A1 (en) | Process for the production of a phthaloperinone | |
| DE2626271A1 (en) | CHINOLINE DERIVATIVES, PROCESS FOR THEIR MANUFACTURING AND USE | |
| Etaiw et al. | Unusual chromic behaviour of the solid supramolecular 3D polymers [(Me3Sn) nFe (CN) 6]∞(n= 34) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |