ORGANYLOXYSILYL-TERMINATED POLYMERS ON THE BASIS OF 1,3-DIOXOLANE COPOLYMER BUILDING BLOCKS

Abstract

The Applicants respectfully request that the abstract of the instant application be removed in its entirety and replaced with the following wording. Organyloxysilyl-terminated polymers end groups of the formula (I) and 1,3-dioxolane copolymer units (DP) of the general formula (II) in the backbone. Along with methods of producing and uses for the same.

Claims

1-10. (canceled)

11. An organyloxysilyl-terminated polymer (P), comprising: wherein the organyloxysilyl-terminated polymer (P) has end groups of the formula (I)
(CR.sup.1.sub.2).sub.bSiR.sub.a(OR.sup.2).sub.3-a(I); wherein R may be identical or different and is a monovalent, unsubstituted or substituted, SiC-bonded hydrocarbon radical; wherein R.sup.1 may be identical or different and is a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon radical; wherein R.sup.2 may be identical or different and is a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon radical; wherein a may be identical or different and is 0, 1 or 2; and wherein b may be identical or different and is an integer from 1 to 10; wherein the organyloxysilyl-terminated polymer (P) further comprises 1,3-dioxolane copolymer units (DP) of the general formula (II) in the backbone thereof
[(OCH.sub.2OCH.sub.2CH.sub.2).sub.x1(OCH.sub.2CH.sub.2OCH.sub.2).sub.x2(OCH.sub.2OCHR.sup.3CHR.sup.4).sub.y1(OCHR.sup.3CHR.sup.4OCH.sub.2)].sub.y2O(II), wherein R.sup.3 may be identical or different and is hydrogen or a monovalent, unsubstituted or substituted C.sub.1- to C.sub.18-alkyl radical; wherein R.sup.4 may be identical or different and is hydrogen or a monovalent, unsubstituted or substituted C.sub.1- to C.sub.18-alkyl radical; wherein x1+x2 has values of 10 to 2000; wherein y1+y2 has values of 3+(x1+x2+y1+y2)/100 to 90+(x1+x2+y1+y2)/100; and wherein the [OCH.sub.2OCHR.sup.3CHR.sup.4-].sub.y1 and [OCHR.sup.3CHR.sup.4OCH.sub.2-].sub.y2 units, in each case at least one radical R.sup.3 or R.sup.4 is a C.sub.1- to C.sub.18-alkyl radical.

12. The organyloxysilyl-terminated polymers (P) of claim 11, wherein R is selected from alkyl radicals having 1 or 2 carbon atoms.

13. The organyloxysilyl-terminated polymers (P) of claim 11, wherein R.sup.1 is a hydrogen atom.

14. The organyloxysilyl-terminated polymers (P) of claim 11, wherein R.sup.2 is selected from methyl radical and ethyl radical.

15. The organyloxysilyl-terminated polymers (P) of claim 11, wherein R.sup.3 and R.sup.4 are selected from hydrogen atoms and C.sub.1- to C.sub.6-alkyl radicals.

16. The organyloxysilyl-terminated polymers (P) of claim 11, wherein in each case only one radical R.sup.3 or R.sup.4 in the [OCH.sub.2OCHR.sup.3CHR.sup.4-]y and [OCHR.sup.3CHR.sup.4OCH.sub.2-].sub.y2 units is a C.sub.1- to C.sub.18-alkyl radical, whereas the other radical is in each case a hydrogen atom.

17. The organyloxysilyl-terminated polymers (P) of claim 11, wherein the 1,3-dioxolane copolymer units (DP) of the formula (II) have a number-average molecular weight M.sub.n between 750 and 300 000 Dalton.

18. The organyloxysilyl-terminated polymers (P) of claim 11, further comprising at least one further constituent selected from (A) nitrogen-containing organosilicon compounds, (B) silicone resins, (C) catalysts, (D) adhesion promoters, (E) water scavengers, (F) fillers, (G) additives and (H) aggregates.

19. The organyloxysilyl-terminated polymers (P) of claim 11, wherein the organyloxysilyl-terminated polymers (P) are used in an adhesive or a sealant.

20. A process (P3) for producing organyloxysilyl-terminated polymers (P), comprising: providing organyloxysilyl-terminated polymers (P), wherein the organyloxysilyl-terminated polymer (P) has end groups of the formula (I)
(CR.sup.1.sub.2).sub.bSiR.sub.a(OR.sup.2).sub.3-a(I); wherein R may be identical or different and is a monovalent, unsubstituted or substituted, SiC-bonded hydrocarbon radical, wherein R.sup.1 may be identical or different and is a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon radical, wherein R.sup.2 may be identical or different and is a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon radical, wherein a may be identical or different and is 0, 1 or 2, and wherein b may be identical or different and is an integer from 1 to 10; wherein the organyloxysilyl-terminated polymer (P) further comprises 1,3-dioxolane copolymer units (DP) of the general formula (II) in the backbone thereof
[(OCH.sub.2OCH.sub.2CH.sub.2).sub.x1(OCH.sub.2CH.sub.2OCH.sub.2).sub.x2(OCH.sub.2OCHR.sup.3CHR.sup.4).sub.y1(OCHR.sup.3CHR.sup.4OCH.sub.2)].sub.y2O(II), wherein R.sup.3 may be identical or different and is hydrogen or a monovalent, unsubstituted or substituted C.sub.1- to C.sub.18-alkyl radical, wherein R.sup.4 may be identical or different and is hydrogen or a monovalent, unsubstituted or substituted C.sub.1- to C.sub.18-alkyl radical, wherein x1+x2 has values of 10 to 2000, wherein y1+y2 has values of 3+(x1+x2+y1+y2)/100 to 90+(x1+x2+y1+y2)/100, and wherein the [OCH.sub.2OCHR.sup.3CHR.sup.4-].sub.y1 and [OCHR.sup.3CHR.sup.40CH.sub.2-].sub.y2 units, in each case at least one radical R.sup.3 or R.sup.4 is a C.sub.1- to C.sub.18-alkyl radical; and wherein hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) of the general formula (III)
H[(OCH.sub.2OCH.sub.2CH.sub.2).sub.x1(OCH.sub.2CH.sub.2OCH.sub.2).sub.x2(OCH.sub.2OCHR.sup.3CHR.sup.4).sub.y1(OCHR.sup.3CHR.sup.4OCH.sub.2)].sub.y2OH(III), are reacted with at least one isocyanate-functional silane of the formula (V)
OCN(CR.sup.1.sub.2).sub.bSiR.sub.a(OR.sup.2).sub.3-a(V), wherein R may be identical or different and is a monovalent, unsubstituted or substituted, SiC-bonded hydrocarbon radical, wherein R.sup.1 may be identical or different and is a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon radical, wherein R.sup.2 may be identical or different and is a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon radical, wherein R.sup.3 may be identical or different and is hydrogen or a monovalent, unsubstituted or substituted C.sub.1- to C.sub.18-alkyl radical, wherein R.sup.4 may be identical or different and is hydrogen or a monovalent, unsubstituted or substituted C.sub.1- to C.sub.18-alkyl radical, wherein x1+x2 has values of 10 to 2000, and wherein y1+y2 has values of 3+(x1+x2+y1+y2)/100 to 90+(x1+x2+y1+y2)/100.

21. The process of claim 20, wherein the organyloxysilyl-terminated polymers (P) further comprises at least one further constituent selected from (A) nitrogen-containing organosilicon compounds, (B) silicone resins, (C) catalysts, (D) adhesion promoters, (E) water scavengers, (F) fillers, (G) additives and (H) aggregates.

22. The process of claim 20, wherein the organyloxysilyl-terminated polymers (P) produced is incorporated within an adhesive or a sealant composition.

23. An adhesive or sealant composition, comprising: wherein the adhesive or sealant composition comprises organyloxysilyl-terminated polymers (P), wherein the organyloxysilyl-terminated polymer (P) has end groups of the formula (I)
(CR.sup.1.sub.2).sub.bSiR.sub.a(OR.sup.2).sub.3-a(I); wherein R may be identical or different and is a monovalent, unsubstituted or substituted, SiC-bonded hydrocarbon radical; wherein R.sup.1 may be identical or different and is a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon radical; wherein R.sup.2 may be identical or different and is a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon radical; wherein a may be identical or different and is 0, 1 or 2; and wherein b may be identical or different and is an integer from 1 to 10; wherein the organyloxysilyl-terminated polymer (P) further comprises 1,3-dioxolane copolymer units (DP) of the general formula (II) in the backbone thereof
[(OCH.sub.2OCH.sub.2CH.sub.2).sub.x1(OCH.sub.2CH.sub.2OCH.sub.2).sub.x2(OCH.sub.2OCHR.sup.3CHR.sup.4).sub.y1(OCHR.sup.3CHR.sup.4OCH.sub.2)].sub.y2O(II), wherein R.sup.3 may be identical or different and is hydrogen or a monovalent, unsubstituted or substituted C.sub.1- to C.sub.18-alkyl radical; wherein R.sup.4 may be identical or different and is hydrogen or a monovalent, unsubstituted or substituted C.sub.1- to C.sub.18-alkyl radical; wherein x1+x2 has values of 10 to 2000; wherein y1+y2 has values of 3.Math.(x1+x2+y1+y2)/100 to 90.Math.(x1+x2+y1+y2)/100; and wherein the [OCH.sub.2OCHR.sup.3CHR.sup.4-].sub.y1 and [OCHR.sup.3CHR.sup.4OCH.sub.2-].sub.y2 units, in each case at least one radical R.sup.3 or R.sup.4 is a C.sub.1- to Cis-alkyl radical.

Description

EXAMPLES

Production Example 1: Production of a 1,3-Dioxolane Copolymer Terminated with Hydroxyl Groups (DP-OH)

[0133] Preparation of the catalyst solution: In a Schlenk flask with septum, 150 ml of dry dichloromethane, 15 ml of ethylene glycol and 1.14 ml of trifluoromethanesulfonic acid are mixed under a nitrogen atmosphere.

[0134] 154 ml of the catalyst solution prepared above are transferred to a laboratory reactor equipped with KPG stirrer, thermometer, nitrogen connection and septum, and temperature-controlled at 23? C. To this solution are added 1.15 kg of 4-ethyl-1,3-dioxolane (10.9 mol) and 770 ml (10.9 mol) of 1,3-dioxolane and the mixture stirred at 23? C. The reaction mixture becomes more viscous during the reaction time and turns pink. After 5 hours, ca. 20 ml of pyridine and 100 ml of dichloromethane are added until the reaction solution decolorizes. The product mixture is washed firstly with heptane and then with water, until a pH of 7 is reached.

[0135] Finally, all volatile constituents are removed under vacuum (1 mbar) and a viscous oil is obtained.

Production Example 2: Production of a Polymer (P) According to the Invention

[0136] In a 1 L three-necked flask equipped with dropping funnel, KPG stirrer and thermometer, 475 g of the 1,3-dioxolane copolymer from example 1 are initially charged, heated to 80? C. and dried for 2 h at a pressure of 10 mbar (vacuum).

[0137] The vacuum is released using nitrogen, and 18.5 g of a-isocyanatomethyl methyldimethoxysilane (GENIOSIL? XL 42, commercially available from Wacker Chemie AG, D-Munich) are added dropwise with stirring over 15 minutes. The temperature remains here at 80? C. Then 0.07 g of a bismuth-containing catalyst (commercially available under the name Borchi-Kat 315 from OMG-Borchers, D-Langenfeld) is added. There is a slight warming of the reaction mixture (<5? C.). The mixture is then stirred at 80? C. for 2 hours. Afterwards, a small isocyanate peak is still present in the IR spectrum of the reaction mixture, corresponding to 2 to 5% of the amount of isocyanate groups originally used.

[0138] The mixture is allowed to cool to 50? C. and 1.3 g of methanol is added at this temperature to eradicate the remaining isocyanate. After 0.5 h, the reaction mixture is allowed to cool to room temperature. An IR spectrum recorded thereafter confirms the absence of isocyanate.

Example 1: Adhesive-Sealant Formulation Based on a Polymer (P) According to the Invention

[0139] 168.0 g of polymer from production example 2 are homogenized in a laboratory planetary mixer from PC-Laborsystem, equipped with two cross-arm mixers, at ca. 25? C., with 8.0 g of vinyltrimethoxysilane (commercially available as GENIOSIL? XL 10 from Wacker Chemie AG, D-Munich) for 2 minutes at 200 rpm.

[0140] Then, 220.0 g of ground calcium carbonate coated with stearic acid, having a mean particle diameter (D50%) of ca. 0.4 ?m (commercially available under the name Omyabond 302 from Omya, D-Cologne) are added and macerated for one minute with stirring at 600 rpm. Finally, 4.0 g of N-[2-aminoethyl]-3-aminopropyltrimethoxysilane (commercially available as GENIOSIL? GF 91 from Wacker Chemie AG, D-Munich) is mixed in for 1 minute at 200 rpm and homogenized for 1 minute at 200 rpm under partial vacuum (ca. 100 mbar) and stirred until bubble-free.

[0141] The composition thus obtained is filled into two 310 ml PE cartridges (ca. 200 g per cartridge) and stored for 24 hours at 20? C. before investigation.

Comparative Example C1

[0142] The Procedure is the Same as in Example 1, but Instead of the polymer of production example 2 according to the invention, the identical amount of a polypropylene glycol silane-terminated at both ends having a mean molar mass (M.sub.n) of 12 000 g/mol and end groups of the formula-OC(?O)NHCH.sub.2SiCH.sub.3 (OCH.sub.3).sub.2 (commercially available under the name GENIOSIL? STP-E10 from Wacker Chemie AG, D-Munich) is used.

Example 2: Adhesive-Sealant Formulation Based on a Polymer (P) According to the Invention

[0143] 116.0 g of polymer from production example 2 are homogenized in a laboratory planetary mixer from PC-Laborsystem, equipped with two cross-arm mixers, at ca. 25? C., with 80 g of a polyethylene glycol butyl-terminated at both ends having a number-average molar mass (M.sub.n) of 300 g/mol (commercially available under the name Polyglycol BB 300 from Clariant, D-Gendorf) and 8.0 g of vinyltrimethoxysilane at 200 rpm for 2 minutes.

[0144] Then, 192.0 g of Omyabond 302 are added and macerated with stirring at 600 rpm for one minute. Finally, 4.0 g of 3-aminopropyltrimethoxysilane (commercially available as GENIOSIL? GF 96 from Wacker Chemie AG, D-Munich) is mixed in for 1 minute at 200 rpm and homogenized for 1 minute at 200 rpm under partial vacuum (ca. 100 mbar) and stirred until bubble-free.

[0145] The composition thus obtained is filled into two 310 ml PE cartridges (ca. 200 g per cartridge) and stored for 24 hours at 20? C. before investigation.

Comparative Example C2

[0146] The procedure is the same as in example 3, but instead of the polymer from production example 2 according to the invention, the identical amount of GENIOSIL? STP-E10 is used.

Example 3: Determination of Property Profiles of the Adhesive-Sealants Produced

[0147] The adhesive-sealants obtained in examples 1 and 2 and comparative examples C.sub.1 and C.sub.2 were allowed to crosslink and investigated with respect to skin formation and mechanical properties thereof. The results can be found in Table 1.

Skin Formation Time (SFT)

[0148] To determine the skin formation time, the crosslinkable compositions obtained in the examples are applied in a 2 mm thick layer on PE film and stored at standard conditions (23? C. and 50% relative humidity). During curing, the skin formation is tested once per minute. For this purpose, a dry laboratory spatula is carefully placed on the surface of the sample and pulled upwards. If the sample sticks to the finger, no skin has yet formed. If no sample remains stuck to the finger, a skin has formed and the time is noted.

Mechanical Properties

[0149] The compositions are each spread on milled-out Teflon? panels to a depth of 2 mm and cured for 2 weeks at 23? C. and 50% relative humidity.

[0150] The Shore A hardness is determined according to DIN 53505. The tensile strength is determined according to DIN 53504-S1. Elongation at break is determined according to DIN 53504-S1. The 100% modulus is determined according to DIN 53504-S1.

TABLE-US-00001 TABLE 1 Example 1 C1* 2 C2* SFT [min] 7 7 25 29 Hardness [Shore A] 59 68 21 40 100% modulus [N/mm] 2.8 3.9 0.6 1.2 Tensile strength [N/mm] 3.4 4.3 1.1 2.4 Elongation at break [%] 133 126 228 190 *non-inventive