* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
To a 500 mL three-necked flask equipped with a constant pressure funnel, magnetic stirrer, Dean-Stark tube and condenser, under nitrogen 124.18 g (0.5 mol) Methacryloxypropyltrimethoxysilane was added, 0.15 g of trifluoromethanesulfonic acid, 0.15 g of BHT was heated to 80 °C and 198.35 g (1.5 mol) of acetoxytrimethylene was added dropwise to the reaction flask through a constant pressure funnel. As the dropwise addition progressed, most of the low boiling by-products were continuously distilled off and collected from the Dean-Stark tube side tube. After completion of the addition, stirring was continued for 1 hour. The reaction product was transferred to a separatory funnel and washed with water (100 mL) six times to obtain a neutral colorless transparent liquid. A small amount of low boiling substance was removed by rotary evaporation under reduced pressure to obtain 198.08 g of methacryloxypropyltris(trimethylsiloxy)silane in a yield of 93.7percent.
Stage #1: at 5 - 10℃; for 1 h; Stage #2: at 5 - 10℃; for 1.5 h;
Example 9 A 1000-ml four necked glass flask equipped with a reflux condenser, thermometer and stirrer was purged with nitrogen. The flask was charged with 406.0 g (2.5 mol) of hexamethyldisiloxane and 64.0 g (2.0 mol) of methanol, and cooled in an ice water bath to an internal temperature below 10°C. To the flask kept at an internal temperature of 5-10°C, 9.8 g (0.1 mol) of conc. sulfuric acid was added dropwise over 30 minutes, and stirring was continued at the temperature for 30 minutes. Subsequently, to the flask kept at an internal temperature of 5-10°C, 248.4 g (1.0 mol) of 3-methacryloxypropyltrimethoxysilane was added dropwise over 30 minutes, and stirring was continued at the temperature for one hour. At an internal temperature of 5-25°C, 72.0 g (4.0 mol) of water was added dropwise over one hour. After the completion of dropwise addition, stirring was continued at 15-25°C for 6.5 hours. The reaction solution was subjected to separatory operation to remove the aqueous layer. The organic layer was washed with water and separated again. The resulting organic layer of the reaction solution was analyzed by GC, finding that the area percent ratio of the main product to monomethoxy and monohydroxy compounds, 3-MAPSi(OSiMe3)3/[3-MAPSi(OMe)(OSiMe3)2 + 3-MAPSi(OH) (OSiMe3)2] was 22.5. The total content of monomethoxy and monohydroxy compounds was 0.044 mol, as determined from the area percents by GC. While the organic layer was kept at a temperature of 20-25°C, 24.5 g (0.25 mol) of conc. sulfuric acid was added dropwise over 15 minutes, and stirring was continued at the temperature for one hour. The organic layer after reaction with sulfuric acid was analyzed by GC, finding that the area percent ratio of the main product to monomethoxy and monohydroxy compounds, 3-MAPSi(OSiMe3)3/[3-MAPSi(OMe)(OSiMe3)2 + 3-MAPSi(OH)(OSiMe3)2] was 358.3. The sulfuric acid layer was removed from the reaction solution, after which the organic layer was washed with water, neutralized with aqueous sodium bicarbonate, and washed with water again. On distillation of the resulting organic layer, 393.5 g (0.93 mol) of 3-methacryloxypropyltris(trimethylsiloxy)silane with a purity of 99.6percent was collected as a fraction having a boiling point of 118.5-120.5°C/0.2 kPa. The yield was 93.1percent.
Stage #1: at -15 - 20℃; Stage #2: at 20℃; for 2 h;
EXAMPLE 1 3-methacryloxypropyltris(trimethylsiloxy)silane In a three-neck flask, 75.4 g (0.47 mol) of hexamethyldisiloxane, 39.9 g (0.67 mol) of acetic acid, 8.7 g of sulfuric acid (conc.) (0.09 mol) and 0.5 g of a 10percent solution of trifluoromethanesulfonic acid in acetic acid (0.0003 mol) are initially introduced and stirred at -15° C. to -5° C. At this temperature, 55.0 g (0.22 mol) of 3-methacryloxypropyltrimethoxysilane (Wacker GENIOSIL.(R). GF 31) are metered in over the course of one hour. The mixture is then heated to room temperature and after-stirred for 2 h. After separating off the acidic lower phase from the organic layer, the organic phase is analyzed by means of GC: the following are found (besides the readily volatile constituents): product 49.6 area percent; monoorganoxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (0.2 area percent); monohydroxy impurity (CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.5 area percent) and 0.5 area percent of the difunctional disiloxane (dimers) [CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O. To reduce the content of monohydroxysilane, at room temperature, 18.7 g (0.11 mol) of hexamethyldisilazane are added (1 h) and after-stirred for 1 h. Following the reaction and neutralization with HMN and removal by filtration of the formed salt, the following constituents are identified in the crude product in the GC besides readily volatile constituents: product (45.5 area percent); monoorganoxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (0.2 area percent); monohydroxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.0 area percent) and 0.3 area percent of the difunctional disiloxane (dimers) [CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O. After distilling off the low-boiling components, the crude product has the following purities: product (97.8 area percent); monoorganoxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (0.2 area percent); monohydroxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.0 area percent) and 0.6 area percent of the difunctional disiloxane (dimers) [CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O. Following distillation and fine filtration (filter candle), the product 3-methacryloxypropyltris(tri-methylsiloxy)silane is obtained in 83percent yield, the following GC contents being obtained: product (99.5 area percent); monoorganoxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (0.2 area percent); monohydroxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.0 area percent) and 0.0 area percent of the difunctional disiloxane (dimers) [CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O.
80%
Stage #1: at 45℃; for 2 h; Stage #2: at 45℃; for 0.333333 h;
EXAMPLE 13-methacryloxypropyltris(trimethylsiloxy)silaneIn a three-neck flask, 80.8 g (0.499 mol) of hexamethyldisiloxane, 39.9 g (0.67 mol) of acetic acid and 0.5 g of a 10percent solution of trifluoromethanesulfonic acid in acetic acid (0.0003 mol) are initially introduced and heated to 45° C. with stirring. Then, over the course of one hour (at 45° C.), 55.0 g (0.22 mol) of 3-methacryloxypropyl-trimethoxysilane (WACKER GENIOSIL.(R). GF 31) are added and after-stirred for 1 h at 45° C. The crude product is analyzed by means of gas chromatography (GC). Besides the readily volatile constituents of the reaction mixture, the following GC contents are found: product (44.3 area percent); monoorganoxy impurity CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (1.1 area percent); monohydroxy impurity CH2CH(CH3)-COO-(CH2)3Si(OSiMe3)2OH (0.6 area percent), and 0.5 area percent of the difunctional disiloxane (dimers) [CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O.At 45° C., 13.1 g (0.167 mol) of acetyl chloride are added to the reaction mixture (over the course of 10 min), before the mixture is after-stirred for 10 min. At room temperature, an acidic phase is separated off from the organic layer before the reaction mixture is analyzed again by gas chromatography. The following are found: product (50.0 area percent); monoorganoxy impurity CH2CH(CH3)-COO-(CH2)3Si(OSiMe3)2OMe (0.1 area percent); monohydroxy impurity CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.5 area percent) and 0.8 area percent of the difunctional disiloxane (dimers) [CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O.In order to eliminate/reduce the remaining content of monohydroxysilane impurity, 18 g (0.12 mol) of hexamethyl-disilazane are added, the reaction mixture being neutralized at the same time. After filtering off the formed salts, the reaction mixture is again analyzed by means of GC. The following are found: product (44.6 area percent); monoorganoxy impurity CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (0.1 area percent); monohydroxy impurity CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.0 area percent) and 0.8 area percent of the difunctional disiloxane (dimers) [CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O.After distilling off the volatile constituents, the product is distilled in vacuo and filtered off via a filter candle. The desired product is obtained in a yield of 80percent and has a purity of 99.6 area percent (contains 0.1 area percent monoorganoxysilane). The specified monohydroxy and disiloxane impurities can no longer be detected.
In methanol; hexane; water; at 20℃; for 3h;Product distribution / selectivity;
4. COMPARATIVE EXAMPLE 5-2; [00160] The same reaction procedures as in Comparative Example 5-1 were repeated except that trimethylchlorosilane was used in place of triethylchlorosilane. GC analysis of the obtained crude product revealed that 3-tris(trimethylsiloxy)silylpropyl methacrylate was obtained at a ratio of 69.8 % in terms of GC area % as a major product.
With pyridine; In methanol; hexane; water; at 2 - 20℃; for 3h;
12. Comparative Example 5-2 The same reaction procedures as in Comparative Example 5-1 were repeated except that trimethylchlorosilane was used in place of triethylchlorosilane. GC analysis of the obtained crude product revealed that 3-tris(trimethylsiloxy)silylpropyl methacrylate was obtained at a ratio of 69.8% in terms of GC area % as a major product.
With 2,6-di-tert-butyl-4-methyl-phenol; water; acetic acid; isopropyl alcohol; at 80℃; for 168h;Reactivity;
EXAMPLE 4-6: HYDROLYSIS RESISTANCE TEST AT 800C[00206] The silicone compounds obtained in the above-described Example 4-1,Example 4-2, and Example 4-3 and Comparative Examples 4-1 and 4-2, as well as a commercially available silicone compound (Comparative Example 4-3) represented by the Formula (4r3) below were tested for their hydrolysis resistance in the presence of a carboxylic acid.[00207] A solution of 0.1 g of the silicone compound, 3.90 g of 2-propanol, 0.24 g of acetic acid, 0.90 g of water and 2 mg of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor was prepared. The obtained solution was heated in an oven at 80 C for 168 hours, and the degree of decomposition was measured by gas chromatography (GC). Taking the GC area % of the peak of the silicone compound at the beginning (0 hr) of the test as 100, the ratios of the GC area % of the peak of the respective silicone compounds at 136 hours from <n="58"/>the beginning of the test are shown in Table 1 in the column indicated by the heading "80 0C."
With 2,6-di-tert-butyl-4-methyl-phenol; water; acetic acid; butan-1-ol; at 90℃; for 168h;Reactivity;
EXAMPLE 4-7: HYDROLYSIS RESISTANCE TEST AT 900C[00208] The same test as in Example 4-6 above was repeated except that n-butanol having a higher boiling point than 2-propanol was used in place of 2-propanol. The results are shown in the column indicated by the heading "90 0C" in Table 1.
4
[ 17096-07-0 ]
[ 24650-42-8 ]
polymer, radical polymerization, degree of polymerization 13530; monomer(s): 2,2-dimethoxy-2-phenyl-acetophenone; 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate[ No CAS ]
polymer, radical polymerization, degree of polymerization 180; monomer(s): 2,2-dimethoxy-2-phenyl-acetophenone; 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate[ No CAS ]
polymer, radical polymerization, degree of polymerization 12470; monomer(s): 2,2-dimethoxy-2-phenyl-acetophenone; 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate[ No CAS ]
polymer, radical polymerization, degree of polymerization 300; monomer(s): 2,2-dimethoxy-2-phenyl-acetophenone; 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate[ No CAS ]
polymer, radical polymerization, degree of polymerization 190; monomer(s): 2,2-dimethoxy-2-phenyl-acetophenone; 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate[ No CAS ]
polymer, radical polymerization, degree of polymerization 7850; monomer(s): 2,2-dimethoxy-2-phenyl-acetophenone; 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate[ No CAS ]
To the similar equipment used in Example 1 were charged 198.6 g (0.47 mol) of 3-methacryloxypropyltris (trimethyl-siloxy) silane, 101.4 g of 3,4,5,6-dibenzo-1,2-oxa phosphophane-2-oxide and 50 g of propionic acid, followed by heating at 150 C. for 17 hours, while stirring and removing the solvent under reduced pressure to obtain 285.0 g of a product. Structure of thus obtained product was identified using GPC, IR absorption spectra, 1H-NMR and mass spectra to confirm that said product was a phosphorus-containing organosilicon compound (D)
poly(3-methacryloyloxypropyltris(trimethylsiloxy)silane (TRIS)-co-n-butyl methacrylate)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With 2,2'-azobis(2-methylbutanenitrile); ethyl acetate; at 72 - 75℃; for 21h;
Poly(3-methacryloyloxypropyltris(trimethylsiloxy)silane(TRIS)-co-methyl methacrylate) (PSS2)-This copolymer was obtained by polymerization of its monomer components in a 25 ml reaction vessel charged with 6 g ethyl acetate, 1.8 g (0.004 mol) TRIS, 0.2 g (0.002 mol) methyl methacrylate, and 0.04 g 2,2'-azobis(2-methylbutanenitrile). The polymerization was run for 21 hours at 72-75 C. The polymer was precipitated into methanol and dried at 50 C.
poly(3-methacryloyloxypropyltris(trimethylsiloxy)silane(TRIS)-co-methyl methacrylate)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With 2,2'-azobis(2-methylbutanenitrile); ethyl acetate; at 72 - 75℃; for 21h;
Poly(3-methacryloyloxypropyltris(trimethylsiloxy)silane(TRIS)-co-methyl methacrylate) (PSS2)-This copolymer was obtained by polymerization of its monomer components in a 25 ml reaction vessel charged with 6 g ethyl acetate, 1.8 g (0.004 mol) TRIS, 0.2 g (0.002 mol) methyl methacrylate, and 0.04 g 2,2'-azobis(2-methylbutanenitrile). The polymerization was run for 21 hours at 72-75 C. The polymer was precipitated into methanol and dried at 50 C.
Introduced into a 1 liter reactor were 300 g of isododecane, then the temperature was increased so as to pass from ambient temperature (25 C.) to 90 C. over 1 hour. Added next, at 90 C. and over 1 hour, were 97.5 g of isobornyl acrylate, 105 g of isobornyl methacrylate, 7.7 g of methacryloxypropyltris(trimethylsiloxy)silane (MPTS) and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 from Akzo Nobel). The mixture was kept at 90 C. for 1 h 30 min.Introduced next to the preceding mixture, still at 90 C. and over 30 minutes were 90 g of isobutyl acrylate and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-di-methylhexane. The mixture was kept at 90 C. for 3 hours, then the whole mixture was cooled.A solution comprising 49.2% of polymer active material in isododecane was obtained. The polymer comprised a first block comprising the isobornyl (meth)acrylates and the silicone monomer and a second block comprising the isobutyl acrylate.
12
1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl acrylate[ No CAS ]
[ 106-63-8 ]
iso-bornyl methacrylate[ No CAS ]
[ 17096-07-0 ]
poly(isobornyl acrylate-co-isobornyl methacrylate-co-isobutyl acrylate-co-methacryloxypropyltris-(trimethoxysiloxy)silane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Introduced into a 1 liter reactor were 300 g of isododecane, then the temperature was increased so as to pass from ambient temperature (25 C.) to 90 C. over 1 hour. Added next, at 90 C. and over 1 hour, were 105 g of isobornyl acrylate, 105 g of isobornyl methacrylate and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 from Akzo Nobel). The mixture was kept at 90 C. for 1 h 30 min.Introduced next to the preceding mixture, still at 90 C. and over 30 minutes were 82.5 g of isobutyl acrylate, 7.5 g of methacryloxypropyltris-(trimethylsiloxy)silane (MPTS) and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane. The mixture was kept at 90 C. for 3 hours, then the whole mixture was cooled.A solution comprising 50.8% of polymer active material in isododecane was obtained. The polymer comprised a first block comprising the isobornyl (meth)acrylates and a second block comprising the silicone monomer and the isobutyl acrylate.
poly(acrylic acid-co-isobornyl acrylate-co-isobornyl methacrylate-co-methacryloxypropyltris(trimethylsiloxy)silane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30 g of isododecane was placed in a 250-ml three-necked flask, then heated to 90 C. In the space of 1 hour, 10.5 g of isobornyl acrylate, 10.5 g of isobornyl methacrylate and 0.19 g of initiator tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S from Akzo Nobel) were added. The whole was maintained at 90 C. for 1.5 h.Then to the aforesaid mixture, at 90 C. and in 30 minutes, 8.25 g of MPTS, 0.75 g of acrylic acid and 0.13 g of Trigonox 21S were added. The mixture was held at 90 C. for 3 hours, then the whole was cooled to 25 C.A 54.6% solution of polymer dry matter in isododecane was obtained. Said polymer comprised a first block comprising isobornyl (meth)acrylates and a second block comprising the silicone monomer and acrylic acid.
poly(acrylic acid-co-isobornyl acrylate-co-isobornyl methacrylate-co-methacryloxypropyltris(trimethylsiloxy)silane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30 g of isododecane was placed in a 250-ml three-necked flask, then heated to 90 C. In the space of 30 minutes, 7.5 g of isobornyl acrylate, 7.5 g of isobornyl methacrylate and 0.33 g of initiator tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S from Akzo Nobel) were added. The whole was maintained at 90 C. for 1.5 h.Then, to the aforesaid mixture, at 90 C. and in 30 minutes, 13.5 g of MPTS, 1.5 g of acrylic acid and 0.22 g of Trigonox 21S were added. The mixture was held at 90 C. for 3 hours, then the whole was cooled to 25 C.A 56.2% solution of polymer dry matter in isododecane was obtained. Said polymer comprised a first block comprising isobornyl (meth)acrylates and a second block comprising the silicone monomer and acrylic acid.
poly(acrylic acid-co-isobornyl acrylate-co-isobornyl methacrylate-co-methacryloxypropyltris(trimethylsiloxy)silane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30 g of isododecane was placed in a 250-ml three-necked flask, then heated to 90 C. In the space of 30 minutes, 4.5 g of isobornyl acrylate, 4.5 g of isobornyl methacrylate and 0.37 g of initiator 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 from Akzo Nobel) were added. The whole was maintained at 90 C. for 1.5 h.Then, to the aforesaid mixture, at 90 C. and in 30 minutes, 19.5 g of MPTS, 1.5 g of acrylic acid and 0.29 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were added. The mixture was held at 90 C. for 3 hours, then the whole was cooled to 25 C.A 55.4% solution of polymer dry matter in isododecane was obtained. Said polymer comprised a first block comprising isobornyl (meth)acrylates and a second block comprising the silicone monomer and acrylic acid.
poly(isobornyl acrylate-co-isobornyl methacrylate-co-methacryloxypropyltris(trimethylsiloxy)silane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30 g of isododecane was placed in a 250-ml three-necked flask, then heated to 90 C. In the space of 30 minutes, 7.5 g of isobornyl acrylate, 7.5 g of isobornyl methacrylate and 0.30 g of initiator 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 from Akzo Nobel) were added. The whole was maintained at 90 C. for 1.5 h.Then, to the aforesaid mixture, at 90 C. and in 30 minutes, 15.2 g of MPTS and 0.20 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were added. The mixture was held at 90 C. for 3 hours, then the whole was cooled to 25 C.A 51.2% solution of polymer dry matter in isododecane was obtained. Said polymer comprised a first block comprising isobornyl (meth)acrylates and a second block comprising the silicone monomer.
poly(isobornyl acrylate-co-isobornyl methacrylate-co-methacryloxypropyltris(trimethylsiloxy)silane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60 g of isododecane was placed in a 250-ml three-necked flask, then heated to 90 C. In the space of 30 minutes, 21 g of isobornyl acrylate, 21 g of isobornyl methacrylate and 0.36 g of initiator 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 from Akzo Nobel) were added. The whole was maintained at 90 C. for 2.5 h.Then, to the aforesaid mixture, at 90 C. and in 30 minutes, 18 g of MPTS and 0.25 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were added. The mixture was held at 90 C. for 3 hours, then the whole was cooled to 25 C.A 53.1% solution of polymer dry matter in isododecane was obtained. Said polymer comprised a first block comprising isobornyl (meth)acrylates and a second block comprising the silicone monomer.
poly(isobornyl acrylate-co-isobornyl methacrylate-co-methacryloxypropyltris(trimethylsiloxy)silane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30 g of isododecane was placed in a 250-ml three-necked flask, then heated to 90 C. In the space of 30 minutes, 4.5 g of isobornyl acrylate, 4.5 g of isobornyl methacrylate and 0.37 g of initiator 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 from Akzo Nobel) were added. The whole was maintained at 90 C. for 1.5 h.Then, to the aforesaid mixture, at 90 C. and in 30 minutes, 21 g of MPTS and 0.29 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were added. The mixture was held at 90 C. for 3 hours, then the Whole was cooled to 25 C.A 51.5% solution of polymer dry matter in isododecane was obtained. Said polymer comprised a first block comprising isobornyl (meth)acrylates and a second block comprising the silicone monomer.
poly(isobornyl methacrylate-co-methacryloxypropyltris(trimethylsiloxy)silane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30 g of isododecane was placed in a 250-ml three-necked flask, then heated to 90 C. In the space of 30 minutes, 15 g of isobornyl methacrylate and 0.30 g of initiator 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 from Akzo Nobel) were added. The whole was maintained at 90 C. for 1.5 h.Then, to the aforesaid mixture, at 90 C. and in 30 minutes, 15 g of MPTS and 0.20 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were added. The mixture was held at 90 C. for 3 hours, then the whole was cooled to 25 C.A 51.7% solution of polymer dry matter in isododecane was obtained. Said polymer comprised a first block comprising isobornyl methacrylate and a second block comprising the silicone monomer.
poly(isobornyl methacrylate-co-methacryloxypropyltris(trimethylsiloxy)silane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30 g of isododecane was placed in a 250-ml three-necked flask, then heated to 90 C. In the space of 30 minutes, 9 g of isobornyl methacrylate and 0.37 g of initiator 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 from Akzo Nobel) were added. The whole was maintained at 90 C. for 1.5 h.Then to the aforesaid mixture, at 90 C. and in 30 minutes, 21 g of MPTS and 0.28 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were added. The mixture was held at 90 C. for 3 hours, then the whole was cooled to 25 C.A 52.3% solution of polymer dry matter in isododecane was obtained. Said polymer comprised a first block comprising isobornyl methacrylate and a second block comprising the silicone monomer.
poly(isobornyl methacrylate-co-methacryloxypropyltris(trimethylsiloxy)silane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30 g of isododecane was placed in a 250-ml three-necked flask, then heated to 90 C. In the space of 30 minutes, 21 g of isobornyl methacrylate and 0.19 g of initiator 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 from Akzo Nobel) were added. The whole was maintained at 90 C. for 1.5 h.Then, to the aforesaid mixture, at 90 C. and in 30 minutes, 9 g of MPTS and 0.12 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were added. The mixture was held at 90 C. for 3 hours, then the whole was cooled to 25 C.A 52.8% solution of polymer dry matter in isododecane was obtained. Said polymer comprised a first block comprising isobornyl methacrylate and a second block comprising the silicone monomer.
Example 9 A 1000-ml four necked glass flask equipped with a reflux condenser, thermometer and stirrer was purged with nitrogen. The flask was charged with 406.0 g (2.5 mol) of hexamethyldisiloxane and 64.0 g (2.0 mol) of methanol, and cooled in an ice water bath to an internal temperature below 10C. To the flask kept at an internal temperature of 5-10C, 9.8 g (0.1 mol) of conc. sulfuric acid was added dropwise over 30 minutes, and stirring was continued at the temperature for 30 minutes. Subsequently, to the flask kept at an internal temperature of 5-10C, 248.4 g (1.0 mol) of 3-methacryloxypropyltrimethoxysilane was added dropwise over 30 minutes, and stirring was continued at the temperature for one hour. At an internal temperature of 5-25C, 72.0 g (4.0 mol) of water was added dropwise over one hour. After the completion of dropwise addition, stirring was continued at 15-25C for 6.5 hours. The reaction solution was subjected to separatory operation to remove the aqueous layer. The organic layer was washed with water and separated again. The resulting organic layer of the reaction solution was analyzed by GC, finding that the area percent ratio of the main product to monomethoxy and monohydroxy compounds, 3-MAPSi(OSiMe3)3/[3-MAPSi(OMe)(OSiMe3)2 + 3-MAPSi(OH) (OSiMe3)2] was 22.5. The total content of monomethoxy and monohydroxy compounds was 0.044 mol, as determined from the area percents by GC. While the organic layer was kept at a temperature of 20-25C, 24.5 g (0.25 mol) of conc. sulfuric acid was added dropwise over 15 minutes, and stirring was continued at the temperature for one hour. The organic layer after reaction with sulfuric acid was analyzed by GC, finding that the area percent ratio of the main product to monomethoxy and monohydroxy compounds, 3-MAPSi(OSiMe3)3/[3-MAPSi(OMe)(OSiMe3)2 + 3-MAPSi(OH)(OSiMe3)2] was 358.3. The sulfuric acid layer was removed from the reaction solution, after which the organic layer was washed with water, neutralized with aqueous sodium bicarbonate, and washed with water again. On distillation of the resulting organic layer, 393.5 g (0.93 mol) of 3-methacryloxypropyltris(trimethylsiloxy)silane with a purity of 99.6% was collected as a fraction having a boiling point of 118.5-120.5C/0.2 kPa. The yield was 93.1%.
EXAMPLE 1 3-methacryloxypropyltris(trimethylsiloxy)silane In a three-neck flask, 75.4 g (0.47 mol) of hexamethyldisiloxane, 39.9 g (0.67 mol) of acetic acid, 8.7 g of sulfuric acid (conc.) (0.09 mol) and 0.5 g of a 10% solution of trifluoromethanesulfonic acid in acetic acid (0.0003 mol) are initially introduced and stirred at -15 C. to -5 C. At this temperature, 55.0 g (0.22 mol) of 3-methacryloxypropyltrimethoxysilane (Wacker GENIOSIL GF 31) are metered in over the course of one hour. The mixture is then heated to room temperature and after-stirred for 2 h. After separating off the acidic lower phase from the organic layer, the organic phase is analyzed by means of GC: the following are found (besides the readily volatile constituents): product 49.6 area %; monoorganoxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (0.2 area %); monohydroxy impurity (CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.5 area %) and 0.5 area % of the difunctional disiloxane (dimers) [CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O. To reduce the content of monohydroxysilane, at room temperature, 18.7 g (0.11 mol) of hexamethyldisilazane are added (1 h) and after-stirred for 1 h. Following the reaction and neutralization with HMN and removal by filtration of the formed salt, the following constituents are identified in the crude product in the GC besides readily volatile constituents: product (45.5 area %); monoorganoxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (0.2 area %); monohydroxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.0 area %) and 0.3 area % of the difunctional disiloxane (dimers) [CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O. After distilling off the low-boiling components, the crude product has the following purities: product (97.8 area %); monoorganoxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (0.2 area %); monohydroxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.0 area %) and 0.6 area % of the difunctional disiloxane (dimers) [CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O. Following distillation and fine filtration (filter candle), the product 3-methacryloxypropyltris(tri-methylsiloxy)silane is obtained in 83% yield, the following GC contents being obtained: product (99.5 area %); monoorganoxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (0.2 area %); monohydroxy impurity CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.0 area %) and 0.0 area % of the difunctional disiloxane (dimers) [CH2=CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O.
80%
EXAMPLE 13-methacryloxypropyltris(trimethylsiloxy)silaneIn a three-neck flask, 80.8 g (0.499 mol) of hexamethyldisiloxane, 39.9 g (0.67 mol) of acetic acid and 0.5 g of a 10% solution of trifluoromethanesulfonic acid in acetic acid (0.0003 mol) are initially introduced and heated to 45 C. with stirring. Then, over the course of one hour (at 45 C.), 55.0 g (0.22 mol) of 3-methacryloxypropyl-trimethoxysilane (WACKER GENIOSIL GF 31) are added and after-stirred for 1 h at 45 C. The crude product is analyzed by means of gas chromatography (GC). Besides the readily volatile constituents of the reaction mixture, the following GC contents are found: product (44.3 area %); monoorganoxy impurity CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (1.1 area %); monohydroxy impurity CH2CH(CH3)-COO-(CH2)3Si(OSiMe3)2OH (0.6 area %), and 0.5 area % of the difunctional disiloxane (dimers) [CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O.At 45 C., 13.1 g (0.167 mol) of acetyl chloride are added to the reaction mixture (over the course of 10 min), before the mixture is after-stirred for 10 min. At room temperature, an acidic phase is separated off from the organic layer before the reaction mixture is analyzed again by gas chromatography. The following are found: product (50.0 area %); monoorganoxy impurity CH2CH(CH3)-COO-(CH2)3Si(OSiMe3)2OMe (0.1 area %); monohydroxy impurity CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.5 area %) and 0.8 area % of the difunctional disiloxane (dimers) [CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O.In order to eliminate/reduce the remaining content of monohydroxysilane impurity, 18 g (0.12 mol) of hexamethyl-disilazane are added, the reaction mixture being neutralized at the same time. After filtering off the formed salts, the reaction mixture is again analyzed by means of GC. The following are found: product (44.6 area %); monoorganoxy impurity CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OMe (0.1 area %); monohydroxy impurity CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2OH (0.0 area %) and 0.8 area % of the difunctional disiloxane (dimers) [CH2CH(CH3)-COO-(CH2)3-Si(OSiMe3)2]O.After distilling off the volatile constituents, the product is distilled in vacuo and filtered off via a filter candle. The desired product is obtained in a yield of 80% and has a purity of 99.6 area % (contains 0.1 area % monoorganoxysilane). The specified monohydroxy and disiloxane impurities can no longer be detected.
poly(methacryloxypropyl tris(trimethylsiloxy)silane-co-methyl methacrylate-co-isooctane-co-isooctylacrylate)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With 2,2'-azobis(isobutyronitrile); at 75 - 100℃; for 30h;
A 1 L resin flask with overhead stirrer, N2 outlet, condenser and thermocouple under a nitrogen atmosphere was charged with 455 mL of isooctane, 111.3 g (0.263 mol) of methacryloxypropyl tris(trimethylsiloxy)silane (TRIS), 81.9 g (0.818 mol) of methyl methacrylate, 16.8 g (0.091 mol) of isooctyl acrylate and 0.315 g of VAZO-67 free radical initiator (obtained from DuPont). The reaction mixture was heated to 75 C. and held at that temperature for 24 hours. During the hold at 75 C., two additional amounts of 0.153 g of VAZO-67 free radical initiator dissolved in 8 g of isooctane were added to the reaction mixture at 12 hours and at 18 hours, respectively. After the 24 hours at 75 C., the reaction mixture was heated to 100 C. and maintained at 100 C. for 6 hours, for a total reaction time of 30 hours. The reaction mixture was then cooled to room temperature. The reaction produced a solution with a siloxane containing polymer.
With trifluorormethanesulfonic acid; 2,6-di-tert-butyl-4-methyl-phenol; at 80℃; for 1h;Dean-Stark; Inert atmosphere;
To a 500 mL three-necked flask equipped with a constant pressure funnel, magnetic stirrer, Dean-Stark tube and condenser, under nitrogen 124.18 g (0.5 mol) Methacryloxypropyltrimethoxysilane was added, 0.15 g of trifluoromethanesulfonic acid, 0.15 g of BHT was heated to 80 C and 198.35 g (1.5 mol) of acetoxytrimethylene was added dropwise to the reaction flask through a constant pressure funnel. As the dropwise addition progressed, most of the low boiling by-products were continuously distilled off and collected from the Dean-Stark tube side tube. After completion of the addition, stirring was continued for 1 hour. The reaction product was transferred to a separatory funnel and washed with water (100 mL) six times to obtain a neutral colorless transparent liquid. A small amount of low boiling substance was removed by rotary evaporation under reduced pressure to obtain 198.08 g of methacryloxypropyltris(trimethylsiloxy)silane in a yield of 93.7%.
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