Process for the manufacturing of a polymer with urethane groups
11780964 · 2023-10-10
Assignee
Inventors
- Peter Rudolf (Ludwigshafen, DE)
- Hans-Josef Thomas (Ludwigshafen, DE)
- Indre Thiel (Ludwigshafen, DE)
- Hannes Blattmann (Cologne, DE)
Cpc classification
International classification
Abstract
Process for the manufacturing of a polymer with urethane groups, wherein in a first alternative a compound A) with at least two five-membered cyclic monothiocarbonate groups and a compound B) with at least two amino groups, selected from primary or secondary amino groups and optionally a compound C) with at least one functional group that reacts with a group —SH are reacted or wherein in a second alternative a compound A) with at least two five-membered cyclic monothiocarbonate groups or a mixture of a compound A) with a compound A1) with one five-membered cyclic monothiocarbonate group and a compound B) with at least two amino groups, selected from primary or secondary amino groups or a compound B1) with one amino group selected from primary or secondary amino groups or mixtures of compounds B) and B1) and a compound C) with at least two functional groups that react with a group —SH or in case of a carbon-carbon triple bond as functional group that react with a group —SH, a compound C) with at least one carbon-carbon triple bond. are reacted.
Claims
1. A process for the manufacturing of a polymer with urethane groups, comprising, in a first alternative: reacting a compound A) with at least two five-membered cyclic monothiocarbonate groups, a compound B) with at least two amino groups, selected from primary or secondary amino groups, and optionally a compound C) with at least one functional group that reacts with a group —SH; or in a second alternative: reacting a compound A) with at least two five-membered cyclic monothiocarbonate groups or a mixture of a compound A) with a compound A1) with one five-membered cyclic monothiocarbonate group, a compound B) with at least two amino groups, selected from primary or secondary amino groups or a compound B1) with one amino group selected from primary or secondary amino groups or mixtures of compounds B) and B1) and a compound C) with at least two functional groups that react with a group —SH or in case of a carbon-carbon triple bond as functional group that react with a group —SH, a compound C) with at least one carbon-carbon triple bond, wherein, in the first alternative or in the second alternative, the compound A) is a compound of formula I: ##STR00035## wherein R.sup.1 or R.sup.2 is a linking group to Z, three of the groups R.sup.1 to R.sup.4 are hydrogen, n is an integral number of at least 2, and Z is an n-valent organic group.
2. The process according to claim 1, wherein the linking group is simply a bond or a group CH.sub.2—O— or CH.sub.2—O—C(═O)—.
3. The process according to claim 1, wherein Z is a n-valent organic group with up to 50 carbon atoms and may comprise oxygen and n is an integral number from 2 to 5.
4. The process according to claim 1, wherein n is 2.
5. The process according to claim 1, wherein Z is a polyalkoxylene group of formula G1:
(V—O—).sub.mV (G1) wherein V represents a C2-to C20 alkylen group and m is an integral number of at least 1, and whereby the terminal alkylene groups V are bonded to the linking group, which is one of the groups R.sup.1 to R.sup.2.
6. The process according to claim 1, wherein Z is a group of formula G2: ##STR00036## wherein W is a bi-valent organic group with at maximum 10 carbon atoms and R.sup.10 to R.sup.17 independently from each other represent H or a C1- to C4 alkyl group and wherein the two hydrogen atoms in the para position to W are replaced by the bond to the linking group, which is one of the groups R.sup.1 to R.sup.2.
7. The process according to claim 1, wherein Z is a group G3 which is an alkylene group.
8. The process according to claim 1, wherein compound B is a compound B) with at least two aliphatic or cycloaliphatic primary amino groups.
9. The process according to claim 1, wherein compound C) is present and wherein the functional group of compound C) that reacts with —SH is selected from non-aromatic, ethylenically unsaturated groups, epoxy groups, isocyanate groups, groups with a non-aromatic carbon-nitrogen double bond, carbonyl groups or halides.
10. The process according to claim 9, wherein compound C) is present and wherein the functional group of compound C) that reacts with —SH is selected from non-aromatic, ethylenically unsaturated groups or epoxy groups.
11. The process according to claim 9, wherein compound C) is present and wherein the functional group of compound C) that reacts with —SH is a methacryl group.
12. The process according to claim 1, wherein in the second alternative a solution of compound A) and A1) is used.
13. The process according to claim 1, wherein in both alternatives the reaction is carried out in one step by reacting all compounds simultaneously.
14. The process according to claim 1, wherein in both alternatives the reaction is carried out in two steps, in the first alternative ley first reacting A) and B) and then reacting the obtained intermediate with C), and in the second alternative by first reacting A) or mixtures of A) and A1) and B) or B1) or mixtures of B) and B1) and then reacting the obtained intermediate with C).
15. A polymer with urethane groups obtained by a process according to claim 1.
16. A curable composition comprising: a compound A) with at least two five-membered cyclic monothiocarbonate groups, a compound B) With at least two a o groups, selected from primary or secondary amino groups, and optionally a compound C) which at least one functional group that reacts with a group —SH; or comprising the reaction product of the two compounds A) and B) and, in addition, C), wherein the compound A) is a compound of formula I: ##STR00037## wherein R.sup.1 or R.sup.2 is a linking group to Z, three of the groups R.sup.1 to R.sup.4 are hydrogen, n is an integral number of at least 2, and Z is an n-valent organic group.
17. A curable composition comprising: a compound A) with at least two five-membered cyclic monothiocarbonate groups or a mixture of a compound A) with a compound A1) with one five-membered cyclic monothiocarbonate group, a compound B) with at least two amino groups, selected from primary or secondary amino groups or a compound B 1) with one amino group selected from primary or secondary amino groups or mixtures of compounds B) and B1), and a compound C) with at least two functional groups that react with a group —SH or in case of a carbon-carbon triple bond as functional group that react with a group —SH, with at least one carbon-carbon triple bond; or comprising the reaction product of the compounds A) or the mixture of A) and A1) and B) or B1) or the mixture of B) and B1) and, in addition, C), wherein the compound A) is a compound of formula I: ##STR00038## wherein R.sup.1 or R.sup.2 is a linking group to Z, three of the groups R.sup.1 to R.sup.4 are hydrogen, n is an integral number of at least 2, and Z is an n-valent organic group.
18. A compound of formula I ##STR00039## wherein R.sup.1 or R.sup.2 is a linking group to Z, three of the groups R.sup.1 to R.sup.4 are hydrogen, n is an integral number of at least 2, and Z is a n-valent organic group.
19. A process for the manufacturing of a polymer with urethane groups, comprising, in a first alternative: reacting a compound A) with at least two five-membered cyclic monothiocarbonate groups, a compound B) with at least two amino groups, selected from primary or secondary amino groups, and a compound C) with at least one non-aromatic, ethylenically unsaturated functional group that reacts with a group —SH; or in a second alternative: reacting a compound A) with at least two five-membered cyclic monothiocarbonate groups or a mixture of a compound A) with a compound A1) with one five-membered cyclic monothiocarbonate group, a compound B) with at least two amino groups, selected from primary or secondary amino groups or a compound B1) with one amino group selected from primary or secondary amino groups or mixtures of compounds B) and B1) and a compound C) with at least two non-aromatic, ethylenically unsaturated functional groups that react with a group —SH or in case of a carbon-carbon triple bond as functional group that react with a group —SH, a compound C) with at least one non-aromatic carbon-carbon triple bond.
20. The process of claim 1, wherein the polymer is free of thiourethane groups.
Description
EXAMPLES
(1) Compounds with five-membered cyclic monothiocarbonate groups.
(2) Following compounds with five-membered cyclic monothiocarbonate groups have been used in the examples:
(3) ##STR00014##
Synthesis Examples 1 to 6 for Compounds with Five-Membered Cyclic Monothiocarbonate Groups
(4) First Step: Synthesis of β-Chloro Alkylchlorformates
(5) Epoxide was charged to a reactor and kept at −30° C. The molar amount of epoxide is listed in Table 1. 0.01 mol of tetra(n-butyl ammonium chloride were added per 1 mol of epoxide. Thereafter phosgene is added slowly as the reaction is exothermic. When adding the phosgene the temperature was kept via cooling at the temperature listed in the Table. The time of metering phosgene is listed in the Table. The total amount of phosgene was 1.1 mol per 1 mol of epoxide. When the addition of phosgene was completed the reaction mixture was further stirred for about (2 hours). Unreacted phosgene was removed by nitrogen stripping. No further work-up was necessary. The obtained β-chloro alkylchlorformates could be used directly in the next step which is the formation of the thiocarbonates.
(6) The epoxide, the obtained β-chloro alkylchlorformates and further details of the reaction are listed in Table 1.
(7) The β-chloro alkylchlorformates are obtained in form of two different structural isomers (stereoisomers) a and b
(8) ##STR00015##
(9) The selectivities regarding a and b are listed in the Table 1 as well. The total yield listed in Table 1 is based on the epoxide used as starting material.
(10) TABLE-US-00001 total Synthesis β-chloro selectivity yield example epoxide alkylchlorformates T [° C.] a:b (a + b) [%] 1
(11) In case of synthesis example 5 und 6 the yield and selectivity was determined by 1H- und 13C-NMR.
(12) Second Step: Synthesis of Monothiocarbonates
(13) Synthesis of Substituted Cyclic Mono-Thiocarbonates:
(14) The respective β-chloroalkyl chloroformate from synthesis examples 1 to 4 (50 g) and dichloromethane (50 mL) are placed in a 500 mL 4 neck round bottom flask equipped with a KPG crescent stirrer, dropping funnel, thermometer and a reflux condenser. The solution was cooled down to 0° C. with an ice bath before Na.sub.2S (1 equiv., 15 wt % aqueous solution) was slowly added, maintaining the temperature at 5° C. After the complete addition the ice bath was removed and the reaction mixture allowed to warm to room temperature. After stirring for 4 h the phases were separated and the aqueous phase was extracted with dichloromethane (2×50 mL). The solvent was removed from the combined organic phases under reduced pressure and the residual liquid purified by (Kugelrohr) distillation, yielding the desired cyclic thiocarbonate.
(15) TABLE-US-00002 TABLE 2 Selectivities and isolated yields (purities in brackets) of the various mono- thiocarbonates Area % of GC peak β-chloro of yield of alkylchlor- monothio- monothio- formates carbonate in carbonate and from monothio- relation purity after synthesis carbonate to area of distillation example obtained all GC peaks in brackets 1
Synthesis of Compounds with Two Cyclic Monothiocarbonate Groups:
(16) The respective bis-β-chloroalkyl chloroformiate (50 g) and dichloromethane (50 mL) are placed in a 500 mL 4 neck round bottom flask equipped with a KPG crescent stirrer, dropping funnel, thermometer and a reflux condenser. The solution was cooled down to 0° C. with an ice bath before Na.sub.2S (2 equiv., 15 wt % aqueous solution) was slowly added, maintaining the temperature at 5° C. After the complete addition the ice bath was removed and the reaction mixture allowed to warm to room temperature. After stirring for 2 h the phases were separated and the aqueous phase was extracted with dichloromethane (2×50 mL). The solvent was removed from the combined organic phases under reduced pressure yielding the desired compound with two cyclic monothiocarbonate groups.
(17) TABLE-US-00003 TABLE 3 Selectivities and purities of the various compounds with two cyclic mono-thiocarbonate groups β-chloro area % of GC alkylchlor- peak of formates monothiocarbonate from synthesis in relation to area example monothiocarbonate of all GC peaks 5
Preparation of Polymers
Polymer Example 1: Polymer of Compound A) and B)
(18) To a solution of 1.0 g Bisphenol A dithiocarbonate BPA-TC in 2 g of tetrahydrofuran (THF) 0.23 g of pentamethylene diamine were added. The mixture was stirred at room temperature and subsequently poured in an aluminum mold (diameter 6.5 cm).
(19) Curing was achieved at room temperature (24 h) followed by post curing at 60° C. (4 h). The resulting polymer was further characterized by DSC (glass transition temperature, Tg).
Polymer Example 2: Polymer of A), B) and C)
(20) A solution of 1.0 g BPA-TC in 2 g of THF was mixed with 0.54 g of butandiol dimethacrylate. To the resulting mixture 0.23 g of pentamethylene diamine were added. The mixture was stirred at room temperature and subsequently poured in an aluminum mold (diameter 6.5 cm).
(21) Curing was achieved at room temperature (24 h) followed by post curing at 60° C. (4 h). The resulting elastic polymeric film was further characterized by DSC (glass transition temperature, Tg).
Polymer Example 3: Polymer of A), B1) and C)
(22) A solution of 1.0 g Bisphenol A dithiocarbonate (BPA-TC) in 2 g of THF was mixed with 0.54 g of butandiol dimethacrylate and 0.008 g of Tris(2-carboxyethyl)phosphine hydrochloride (stailizer). To the resulting mixture 0.58 g of octylamine were added. The mixture was stirred at room temperature and subsequently poured in an aluminum mold (diameter 6.5 cm).
(23) Curing was achieved at room temperature (24 h) followed by post curing at 60° C. (4 h). The resulting viscous liquid was further characterized by DSC (glass transition temperature, Tg).
Polymer Example 4: Polymer of A), B1) and C)
(24) A solution of 1.0 g BPA-TC in 2 g of THF was mixed with 0.51 g of trimethylolpropane trimethacrylate. To the resulting mixture 0.58 g of octylamine were added. The mixture was stirred at room temperature and subsequently poured in an aluminum mold (diameter 6.5 cm). Curing was achieved at room temperature (24 h) followed by post curing at 60° C. (4 h). The resuiting polymeric film was further characterized by DSC (glass transition temperature, Tg).
(25) TABLE-US-00004 TABLE 4 glass transition temperatures (Tg) of polymers obtained Polymer of polymer example Tg [° C.] 1 50.6 2 6.9 3 −22.8 4 −4.2
Polymer Example 5: Polymer of A), A1), B) and C)
(26) Under stirring 1 g Bisphenol A dithiocarbonate (0.00217 mol) were dissolved in n-butylglycidylmonothiocarbonate (3.0 g, 0.0157 mol, 1 eq). Trimethylolpropane trimethacrylate (2.26 g) was subsequently added. The mixture was homogenized. To the solution was added 1,5-pentandiamine (1.022 g) via syringe. After 10 second of vigorous stirring at room temperature, the reaction mixture was poured in metal mold (bar-shaped)). The molds were stored at 60° C. for 3 hours and the samples were subsequently released from the molds.
(27) The reaction scheme is as follows:
(28) ##STR00034##
(29) The polymer was obtained as a colorless tack-free solid and as a rigid bar showing high transparency.
Polymer Example 6
(30) polymer of A), A1), B) and C
(31) Bisphenol a Dithiocarbonate (BPA-Dithiocarbonate) and n-Butylglycidyl-Monothiocarbonate, Triamine and Compound C with Double Bond
(32) In a 50 ml flask fitted with a magnetic stirrer 5-(buthoxymethyl)-1,3-oxathiolan-2-one (2.4 g) was combined with trimethylolpropane-trimethacrylat, (1.72 g) and BPA-Dithiocarbonate (0.6 g) and subsequently homogenized. To the stirred solution was rapidly added Tris(2-aminoethyl)amine (0.95 g). The mixture was stirred and homogenized at room temperature. The temperature increased from 25 to 40° C. within 60 seconds and the polymer was cured within 30 min.
Example 7
(33) polymer of A), A1), B) and C
(34) Bisphenol a Dithiocarbonate (BPA-Dithiocarbonate) and n-Butylglycidyl-Monothiocarbonate, Triamine and Compound C with Epoxy Groups
(35) In a 50 ml flask fitted with a magnetic stirrer a mixture of 1,4 dioxane (0.5 g), 5-(buthoxymethyl)-1,3-oxathiolan-2-one (0.48 g) and BPA-Dithiocarbonate (1.15 g) was homogenized at 30° C. and subsequently combined with trimethylolpropane-triglycidylether (0.76 g). After cooling to room temperature to the stirred solution was rapidly added Tris(2-aminoethyl)amine (0.28 g).
(36) The temperature increased and the polymer solidified within 30 min.
Example 8
(37) polymer of A) and B)
(38) Polyethyleneglycol-Dithiocarbonate (PEG-Dithiocarbonate) and Diamine without Compound C
(39) In a 50 ml flask fitted with a magnetic stirrer PEG-Dithiocarbonate (average MW: 620 g/mol, 5,0 g) was combined with 1,3-Bis(aminomethyl)cyclohexane (1.15 g) The temperature increased from 25 to 38° C. within 240 seconds and the polymer solidified within 18 h