Organotin containing hyperbranched polysiloxane structure and preparation method therefor

Abstract

A method of preparing an organotin containing hyperbranched polysiloxane structure includes the following steps: (1) by weight, 0.5-1.5 portions of hyperbranched polysiloxane with reactive functional groups is dissolved in 50-100 portions of an alcohol solvent, to obtain a solution A; (2) by weight, 0.5-0.9 portions of a tin-based initiator and 50-100 portions of the alcohol solvent are mixed to obtain a solution B, wherein said tin-based initiator is selected from dihydroxy butyl tin chloride, butyl tin trichloride, and dibutyl tin dichloride; and (3) dropping the solution B into the solution A at the temperature of 0 C.-60 C., reacting for 3-6 h, filtering and drying to obtain the organotin containing hyperbranched polysiloxane structure.

Claims

1. A method of preparing an organotin containing hyperbranched polysiloxane structure comprising the following steps: (1) by weight, 0.5-1.5 portions of hyperbranched polysiloxane with reactive functional groups is dissolved in 50-100 portions of an alcohol solvent, to obtain a solution A; (2) by weight, 0.5-0.9 portions of a tin-based initiator and 50-100 portions of the alcohol solvent are mixed to obtain a solution B, wherein said tin-based initiator is selected from dihydroxy butyl tin chloride, butyl tin trichloride, and dibutyl tin dichloride; and (3) dropping the solution B into the solution A at the temperature of 0 C.-60 C., reacting for 3-6 h, filtering and drying to obtain the organotin containing hyperbranched polysiloxane structure.

2. The method according to claim 1, wherein said hyperbranched siloxane with active functional groups has a molecular weight of 3500 to 9312, and the active functional groups are selected from an amino group, an epoxy group, a vinyl group, and a combination thereof.

3. The method according to claim 1, wherein said alcohol solution is isopropanol, ethanol, or a combination thereof.

4. An organotin containing hyperbranched polysiloxane structure obtained by the method according to claim 1.

Description

DESCRIPTION OF FIGURES

(1) FIG. 1 illustrates the structure of the organotin with hyperbranched polysiloxane.

(2) FIG. 2 is the fourier transform infrared (FTIR) spectra of 3-triethoxysilylpropylamine, amino-terminated hyperbranched polysiloxane, dihydroxy butyl tin chloride, and organotin with hyperbranched polysiloxane prepared in Example 1.

(3) FIG. 3 shows the .sup.1H NMR spectrum of amino-terminated hyperbranched polysiloxane prepared in Example 1.

(4) FIG. 4 shows .sup.29Si NMR spectra of amino-terminated hyperbranched polysiloxane and the new organotin (HSiSn) prepared in Example 1.

(5) FIG. 5 gives DSC curves of cyanate ester prepolymer with dihydroxy butyl tin chloride (BCD/CE), and that with the organotin (HSiSn/CE) prepared in Example 1.

(6) FIG. 6 shows TG and DTG curves of cured cyanate ester resin with dihydroxy butyl tin chloride (BCD/CE), and that with the new organotin (HSiSn/CE) prepared in Example 1.

DETAILED DESCRIPTION OF THE INVENTION

(7) The technical solution of the present invention will be described in further details with reference to the drawings and examples.

Example 1

(8) The synthesis of an organotin with amino-terminated hyperbranched polysiloxane follows the steps described below.

(9) 1. The synthesis of amino-terminated hyperbranched polysiloxane.

(10) 22.1 g 3-triethoxysilylpropylamine (APTES) and 2.0 g distilled water are homogeneously mixed at room temperature. After 15 min of magnetic stirring, the solution is slowly heated to 60 C. and reacting for 4 h. After the reaction is completed, through vacuum drying to steam out ethanol, a transparent viscous amino-terminated hyperbranched polysiloxane is obtained. Its molecular weight is 6918.

(11) 2. The synthesis of organotin with amino-terminated hyperbranched polysiloxane.

(12) 1.34 g amino-terminated hyperbranched polysiloxane obtained in step 1 is dissolved in 50 mL isopropanol to form a solution; the solution is slowly heated to 55 C., and then into which 50 mL isopropanol containing 0.7 g dihydroxy butyl tin chloride (BCD) is dropped, then the solution is remained at 55 C. while stirring for 5 h. After filtering and drying, an organotin containing amino-terminated hyperbranched polysiloxane is obtained, in which the tin content is 0.121 wt %. The synthesis procedure, infrared spectroscopy, .sup.1H NMR and .sup.29Si NMR spectra of the organotin is shown in FIGS. 1, 2, 3 and 4.

(13) Referring to FIG. 1, which is a schematic representation of the synthesis of organotin with amino-terminated hyperbranched polysiloxane provide in this example. It can be seen that the organotin with amino-terminated hyperbranched polysiloxane is halogen-free.

(14) FIG. 2 gives the FTIR spectra of 3-triethoxysilylpropylamine (APTES), amino-terminated hyperbranched polysiloxane (AHBSi), dihydroxy butyl tin chloride (BCD) and organotin with amino-terminated hyperbranched polysiloxane (HsiSn). There is a broad and overlapped absorption band attributing to SiOSi groups from 1000 to 1200 cm.sup.1 in the spectrum of AHBSi; meanwhile, a broad and overlapped absorption band appeared at 3419 cm.sup.1 indicating the hydrolysis of ethoxy to form silanol.

(15) In addition, the absorption peaks at 926 cm.sup.1 (for SiOH of AHBSi and SnOH of BCD) and 554 cm.sup.1 (SnCl of BCD) are not observed, instead, a new absorption peak at 770 cm.sup.1 (SiOSn) appears, clearly manifesting the synthesis of HsiSn.

(16) FIG. 3 shows the .sup.1H NMR spectrum of AHBSi, the chemical shift at 3.7 ppm is assigned to the OH group, this further validates the polycondensation. In addition, the chemical shift of amine at 1.5 ppm is also observed.

(17) FIG. 4 shows the .sup.29Si NMR spectra of AHBSi and HsiSn obtained in this example, the spectrum of HSiSn shows the chemical shifts representing dendritic unit, linear unit and terminal unit, suggesting that HSiSn has hyperbranched structure. Especially, compared with the T shift (53.60 ppm) in the spectrum of AHBSi, that of HSiSn appears at 48.71 ppm due to the condensation between AHBSi and butyltin chloride dihydroxide. The degree of branch (DB) of AHBSi was calculated to be 0.80.

(18) From the results of FIG. 2-4, it is confirmed that AHBSi was successfully synthesized.

(19) From the results of FIGS. 2 and 4, it can be confirmed that HSiSn was obtained.

(20) On the base of successful synthesis of HSiSn, the modified cyanate ester (CE) resin was prepared according to following process. Specifically, 100 g 2,2-bis(4-cyanatophenyl)propane (commercial CE monomer of bisphenol A type) was heated to 90 C. to get completely molten CE, into which 0.064 g HSiSn obtained above was added; after stirring at 90 C. for 20 min, a modified CE prepolymer (HSiSn/CE) was obtained. The DSC curve of HSiSn/CE prepolymer with a heating rate of 10 C./min under a nitrogen atmosphere is shown in FIG. 5. The prepolymer was put into a preheated mold and thoroughly degassed to remove entrapped air at 120 C. in a vacuum oven, and then the mold was put into an oven for curing and postcuring following the protocol of 150 C./2 h+180 C./2 h+200 C./2 h+220 C./2 h+240 C./4 h, successively, to obtain a cured resin. FIG. 6 shows the TG and DTG curves of the cured HSiSn/CE resin with a flow rate of 100 mL/min and a heating rate of 10 C./min. The temperature at which the weight loss of a sample reaches 5 wt % is regarded as the initial decomposition temperature (T.sub.di) the char yield at 800 C. is coded as Y.sub.c.

(21) The CE resin modified by BCD was also prepared using following steps. 100 g 2,2-bis(4-cyanatophenyl)propane is heated to 90 C. to get a completely molten liquid CE, into which 0.032 g BCD was added; after stirring at 90 C. for 20 min, a BCD/CE prepolymer was obtained. FIG. 5 gives the DSC curve of BCD/CE prepolymer with a heating rate of 10 C./min under a nitrogen atmosphere. The BCD/CE prepolymer was put into a preheated mold and thoroughly degassed to remove entrapped air at 120 C. in a vacuum oven, and then the mold was put into an oven for curing and postcuring following the protocol of 150 C./2 h+180 C./2 h+200 C./2 h+220 C./2 h+240 C./4 h, successively, to obtain a cured resin. FIG. 6 shows the TG and DTG curves of cured BCD/CE resin with a flow rate of 100 mL/min and a heating rate of 10 C./min.

(22) By contrast the curves in FIG. 5, it can be seen that in the curve of BCD/CE prepolymer, a curing peak appears just behind the melting peak, so the gap between the melting and curing temperatures is narrow, and this phenomenon means a relatively poor processing feature because it is generally to get cured structure without uniform structure and good performance. In addition, the curve of BCD/CE prepolymer shows multiple curing peaks, indicating that BCD has poor dispersion in CE resin, so there are different parts that have different curing reactivity. While attractively, this poor phenomenon does not appear in the DSC curve of HSiSn/CE prepolymer. In detail, the temperature gap between the curing peak and the melting peak is wide, so there is a wide processing window for HSiSn/CE prepolymer. In addition, compared with the curing peak in the DSC curve of CE, that of HSiSn/CE prepolymer shows an obvious shift toward lower temperature, demonstrating that HSiSn has an appropriate and good catalytic reactivity.

(23) FIG. 6 gives TG and DTG curves of cured BCD/CE and HSiSn/CE resins. The two cured resins have almost same initial decomposition temperatures (T.sub.di, 420 C.), but they have an obviously different char yields, the char yields of HSiSn/CE and BCD/CE resins are 45.6 wt % and 40.8 wt %, respectively. The temperature at which showing the maximum decomposition rate of HSiSn/CE resin is 437 C. and that of BCD/CE resin is 443 C. All these results demonstrate that HSiSn/CE resin has better thermal stability than BCD/CE resin. This attractive result can be contributed to the outstanding thermal stability and catalytic reactivity of hyperbranched polysiloxane.

Example 2

(24) 1. The synthesis of epoxy-terminated hyperbranched polysiloxane.

(25) 47.3 g 3-glycidoxypropyltrimethoxysilane, 4.0 g distilled water, and 100 mL ethanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution, and then 1 mL HCl (36.5%) was added into the flask. After being maintained at room temperature for 15 min, the solution was heated to 50 C. and maintained at 50 C. with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off ethanol. Finally, a transparent and viscous liquid was obtained, which was epoxy-terminated hyperbranched polysiloxane, and the molecular weight is 7500.

(26) 2. The synthesis of new organotin.

(27) 1.34 g epoxy-terminated hyperbranched polysiloxane was dissolved in 50 mL isopropanol to form a solution A; after being maintained at room temperature for 15 min, the solution A was heated to 55 C., and then into which 50 mL isopropanol which contained 0.7 g dihydroxy butyl tin chloride was added to get a mixture B. The mixture B was stayed at 55 C. with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.26 wt %.

Example 3

(28) The synthesis of the new organotin follows the steps described below.

(29) 1. The synthesis of vinyl-terminated hyperbranched polysiloxane.

(30) 28.0 g vinyltris(2-methoxyethoxy)silane, 1.98 g distilled water, and 100 mL ethanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution, and then 1 mL HCl (36.5%) was added into the flask. After being maintained at room temperature for 15 min, the solution was heated to 50 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off ethanol. Finally, a transparent and viscous liquid was obtained, which was vinyl-terminated hyperbranched polysiloxane, and the molecular weight is 4200.

(31) 2. The synthesis of the new organotin.

(32) 0.5 g vinyl-terminated hyperbranched polysiloxane was dissolved in 50 mL isopropanol; after being maintained at room temperature for 15 min, the solution was heated to 55 C., and then into which 50 mL isopropanol which contained 0.5 g dihydroxy butyl tin chloride was added to get a mixture B. The mixture B was stayed at 55 C. with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.32 wt %.

Example 4

(33) The synthesis of the new organotin follows the steps described below.

(34) 1. The synthesis of epoxy-terminated hyperbranched polysiloxane.

(35) 45.3 g 3-glycidoxypropyltrimethoxysilane, 4.0 g distilled water, and 100 mL ethanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution, and then 1 mL HCl (36.5%) was added into the flask. After being maintained at room temperature for 15 min, the solution was heated to 50 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off ethanol. Finally, a transparent and viscous liquid was obtained, which was epoxy-terminated hyperbranched polysiloxane, and the molecular weight is 7140.

(36) 2. The synthesis of the new organotin.

(37) 1.25 g epoxy-terminated hyperbranched polysiloxane was dissolved in 60 mL isopropanol; after being maintained at room temperature for 15 min, the solution was heated to 55 C., and then into which 50 mL isopropanol which contained 0.5 g dihydroxy butyl tin chloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.11 wt %.

Example 5

(38) The synthesis of the new organotin follows the steps described below.

(39) 1. The synthesis of amino-terminated hyperbranched polysiloxane.

(40) 17.9 g 3-triethoxysilylpropylamine, 2.2 g distilled water, and 100 mL methanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution. After being maintained at room temperature for 15 min, the solution was heated to 60 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off methanol. Finally, a transparent and viscous liquid was obtained, which was amino-terminated hyperbranched polysiloxane, signed as AHBSi, and the molecular weight is 5120.

(41) 2. The synthesis of the new organotin.

(42) 0.90 g AHBSi was dissolved in 50 mL ethanol; after being maintained at room temperature for 15 min, the solution was cooled to 5 C., and then into which 100 mL ethanol which contained 0.9 g dibutyl tin dichloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.3 wt %.

Example 6

(43) The synthesis of the new organotin follows the steps described below.

(44) 1. The synthesis of epoxy-terminated hyperbranched polysiloxane.

(45) 47.3 g 3-glycidoxypropyltrimethoxysilane, 3.5 g distilled water, and 100 mL ethanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution, and then 1 mL HCl (36.5%) was added into the flask. After being maintained at room temperature for 15 min, the solution was heated to 50 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off ethanol. Finally, a transparent and viscous liquid was obtained, which was epoxy-terminated hyperbranched polysiloxane, and the molecular weight is 7630.

(46) 2. The synthesis of the new organotin.

(47) 1.4 g epoxy-terminated hyperbranched polysiloxane was dissolved in 80 mL isopropanol; after being maintained at room temperature for 15 min, the solution was cooled to 5 C., and then into which 100 mL ethanol which contained 0.6 g dibutyl tin dichloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.256 wt %.

Example 7

(48) The synthesis of the new organotin follows the steps described below.

(49) 1. The synthesis of vinyl-terminated hyperbranched polysiloxane.

(50) 27.0 g vinyltris(2-methoxyethoxy)silane, 1.98 g distilled water, and 100 mL ethanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution, and then 1 mL HCl (36.5%) was added into the flask. After being maintained at room temperature for 15 min, the solution was heated to 50 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off ethanol. Finally, a transparent and viscous liquid was obtained, which was vinyl-terminated hyperbranched polysiloxane, and the molecular weight is 3800.

(51) 2. The synthesis of the new organotin.

(52) 0.5 g vinyl-terminated hyperbranched polysiloxane was dissolved in 50 mL ethanol; after being maintained at room temperature for 15 min, the solution was heated to 60 C., and then into which 50 mL isopropanol which contained 0.7 g dihydroxy butyl tin chloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.24 wt %.

Example 8

(53) The synthesis of the new organotin follows the steps described below.

(54) 1. The synthesis of epoxy-terminated hyperbranched polysiloxane.

(55) 40.3 g 3-glycidoxypropyltrimethoxysilane, 4.0 g distilled water, and 100 mL ethanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution, and then 1 mL HCl (36.5%) was added into the flask. After being maintained at room temperature for 15 min, the solution was heated to 50 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off ethanol. Finally, a transparent and viscous liquid was obtained, which was epoxy-terminated hyperbranched polysiloxane, and the molecular weight is 6930.

(56) 2. The synthesis of the new organotin.

(57) 1.1 g epoxy-terminated hyperbranched polysiloxane was dissolved in 50 mL ethanol; after being maintained at room temperature for 15 min, the solution was cooled to 5 C., and then into which 100 mL ethanol which contained 0.8 g dihydroxy butyl tin chloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product.

(58) The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.189 wt %.

Example 9

(59) The synthesis of the new organotin follows the steps described below.

(60) 1. The synthesis of amino-terminated hyperbranched polysiloxane.

(61) 22.1 g 3-triethoxysilylpropylamine, 1.9 g distilled water, and 100 mL methanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution. After being maintained at room temperature for 15 min, the solution was heated to 60 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off methanol. Finally, a transparent and viscous liquid was obtained, which was amino-terminated hyperbranched polysiloxane, signed as AHBSi, and the molecular weight is 6708.

(62) 2. The synthesis of the new organotin.

(63) 1.3 g AHBSi was dissolved in 100 mL ethanol; after being maintained at room temperature for 15 min, the solution was heated to 55 C., and then into which 90 mL isopropanol which contained 0.6 g dihydroxy butyl tin chloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.145 wt %.

Example 10

(64) The synthesis of the new organotin follows the steps described below.

(65) 1. The synthesis of amino-terminated hyperbranched polysiloxane.

(66) 19.7 g 3-triethoxysilylpropylamine, 2.6 g distilled water, and 100 mL methanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution. After being maintained at room temperature for 15 min, the solution was heated to 60 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off methanol. Finally, a transparent and viscous liquid was obtained, which was amino-terminated hyperbranched polysiloxane, signed as AHBSi, and the molecular weight is 9312.

(67) 2. The synthesis of the new organotin.

(68) 1.27 g AHBSi was dissolved in 70 mL ethanol; after being maintained at room temperature for 15 min, the solution was cooled to 0 C., and then into which 100 mL isopropanol which contained 0.6 g butyl tin chloride 0.90 g AHBSi was dissolved in 50 mL ethanol, after being maintained at room temperature for 15 min, the solution was cooled to 5 C., and then into which 100 mL ethanol which contained 0.9 g dibutyl tin dichloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.135 wt %.

Example 11

(69) The synthesis of the new organotin follows the steps described below.

(70) 1. The synthesis of epoxy-terminated hyperbranched polysiloxane.

(71) 50.3 g 3-glycidoxypropyltrimethoxysilane, 4.0 g distilled water, and 100 mL ethanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution, and then 1 mL HCl (36.5%) was added into the flask. After being maintained at room temperature for 15 min, the solution was heated to 50 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off ethanol. Finally, a transparent and viscous liquid was obtained, which was epoxy-terminated hyperbranched polysiloxane, and the molecular weight is 7800.

(72) 2. The synthesis of the new organotin.

(73) 1.4 g epoxy-terminated hyperbranched polysiloxane was dissolved in 100 mL isopropanol; after being maintained at room temperature for 15 min, the solution was cooled to 5 C., and then into which 90 mL ethanol which contained 0.8 g dibutyl tin dichloride 0.90 g AHBSi was dissolved in 50 mL ethanol, after being maintained at room temperature for 15 min, the solution was cooled to 5 C., and then into which 100 mL ethanol which contained 0.9 g dibutyl tin dichloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.142 wt %.

Example 12

(74) The synthesis of the new organotin follows the steps described below.

(75) 1. The synthesis of vinyl-terminated hyperbranched polysiloxane.

(76) 29.0 g vinyltris(2-methoxyethoxy)silane, 1.98 g distilled water, and 100 mL ethanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution, and then 1 mL HCl (36.5%) was added into the flask. After being maintained at room temperature for 15 min, the solution was heated to 50 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off ethanol. Finally, a transparent and viscous liquid was obtained, which was vinyl-terminated hyperbranched polysiloxane, and the molecular weight is 5000.

(77) 2. The synthesis of the new organotin.

(78) 1.4 g vinyl-terminated hyperbranched polysiloxane was dissolved in 100 mL isopropanol; after being maintained at room temperature for 15 min, the solution was cooled to 0 C., and then into which 50 mL isopropanol which contained 0.7 g butyl tin chloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.171 wt %.

Example 13

(79) The synthesis of the new organotin follows the steps described below.

(80) 1. The synthesis of vinyl-terminated hyperbranched polysiloxane.

(81) 24.0 g vinyltris(2-methoxyethoxy)silane, 1.98 g distilled water, and 100 mL ethanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution, and then 1 mL HCl (36.5%) was added into the flask. After being maintained at room temperature for 15 min, the solution was heated to 50 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off ethanol. Finally, a transparent and viscous liquid was obtained, which was vinyl-terminated hyperbranched polysiloxane, and the molecular weight is 3500.

(82) 2. The synthesis of the new organotin.

(83) 1.2 g vinyl-terminated hyperbranched polysiloxane was dissolved in 50 mL isopropanol; after being maintained at room temperature for 15 min, the solution was cooled to 5 C., and then into which 50 mL isopropanol which contained 0.5 g dibutyl tin dichloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 3 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.175 wt %.

Example 14

(84) The synthesis of the new organotin follows the steps described below.

(85) 1. The synthesis of epoxy-terminated hyperbranched polysiloxane.

(86) 47.3 g 3-glycidoxypropyltrimethoxysilane, 3.5 g distilled water, and 100 mL ethanol were put into a three-necked flask equipped with a thermometer and condenser to form a solution, and then 1 mL HCl (36.5%) was added into the flask. After being maintained at room temperature for 15 min, the solution was heated to 50 C. and maintained at that temperature with stirring for 4 h, and then the resultant product was put into a vacuum oven to give off ethanol. Finally, a transparent and viscous liquid was obtained, which was epoxy-terminated hyperbranched polysiloxane, and the molecular weight is 7630.

(87) 2. The synthesis of the new organotin.

(88) 1.4 g epoxy-terminated hyperbranched polysiloxane was dissolved in 80 mL isopropanol; after being maintained at room temperature for 15 min, the solution was cooled to 0 C., and then into which 100 mL ethanol which contained 0.6 g butyl tin chloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.184 wt %.

Example 15

(89) 0.7 g epoxy-terminated hyperbranched polysiloxane from the Example 14 and 0.7 g vinyl-terminated hyperbranched polysiloxane from the Example 12 were dissolved in 80 mL isopropanol; after being maintained at room temperature for 15 min, the solution was cooled to 0 C., and then into which 100 mL ethanol which contained 0.6 g butyl tin chloride was added to get a mixture B. The mixture B was stayed at that temperature with stirring for 5 h to get a crude product. The crude product was filtrated, and the resultant filter cake was dried in vacuo to obtain a new organotin containing hyperbranched polysiloxane, which was designed as HSiSn. The tin content of HSiSn is 0.126 wt %.