CN107400239A - A kind of trapezoidal/cage type polysiloxanes of end-blocking and its preparation method and application certainly - Google Patents

Abstract

The present invention relates to a self-blocking ladder/cage polysiloxane and its preparation method and application. The self-blocking polysiloxane comprises the self-blocking ladder polysiloxane (a) and the self-blocking polysiloxane Cage polysiloxane (b), and the mole percentage of polysiloxane (a) and polysiloxane (b) is greater than or equal to 50 mol%. The polysiloxane of the present invention has higher high temperature resistance (such as the temperature of 5% weight loss under nitrogen atmosphere is greater than 430 ℃, preferably greater than 450 ℃, also preferably greater than 460 ℃) and light transmittance (such as light transmittance greater than 90%; the refractive index is 1.500-1.600, preferably 1.520-1.560), and has solubility and meltability. When mixed with other materials, it will not bring side reactions due to end groups.

Description

A kind of self-blocking trapezoid/cage polysiloxane and its preparation method and application

technical field

The invention relates to a polysiloxane and its preparation method and application, in particular to a trapezoidal/cage polysiloxane and its preparation method and application, belonging to the technical field of polymers.

Background technique

Polysiloxanes with ladder or cage structure, most of the previously reported polysilsesquioxane types, that is, the molecular skeleton is composed of (-RSiO _1.5 -) repeating chain links (wherein R is an organic group). As early as the 1960s, there were reports about trapezoidal polysilsesquioxanes and cage polysilsesquioxanes [J.Am.Chem.Soc.1960, 82(23):6194; J.Am.Chem. Soc. 1946, 68:356; and J. Am. Chem. Soc. 1965, 87:4313]. They are generally obtained from trifunctional silanes through hydrolytic condensation under specific conditions. Different from ordinary trifunctional silane hydrolysis and condensation to obtain random branched products or crosslinked products, under specific conditions, they obtained molecular self-assembly and polymerization to form polymers with a certain regular structure.

As the name implies, the molecular structure of ladder-PSSQ is a ladder-like structure formed by bridging groups, in which -O- connects the siloxane main chain to form a double main chain or multiple main chain structure , and the compositional structure connecting the main chain is vividly called "bridge base". For polysilsesquioxane, the bridging group is "-O-".

Ladder-PSSQ can be dispersed in solvents, other small molecular compounds or polymers at the molecular level. Its inorganic component skeleton composed of silicon and oxygen elements, combined with organic side groups, has dual characteristics of organic materials and inorganic materials, and has excellent properties. High temperature resistance, radiation resistance, excellent electrical insulation, high chemical stability, good hydrophobic and moisture resistance, widely used in semiconductor materials, optical materials and polymer modification.

In 1960, Brown et al first reported the preparation of a double-chain soluble phenyl ladder polysilsesquioxane (PPSQ) from a trifunctional silane monomer by an equilibrium condensation method. Subsequently, people published articles and patents using similar methods to prepare ladder polysilsesquioxanes (R-LPSQ, R is a side group) with different side groups. For example, US Pat. No. 3,017,386 discloses a soluble phenyl polysilsesquioxane with a ladder structure and a preparation method thereof. US Patent 5081202, US Patent 6153689 and Japanese Patent 200159892 also disclose the synthesis of ladder polysilsesquioxanes with different side groups using trichlorosilane. In the 1990s, Zhang Rongben and others proposed a method for preparing ladder-PSSQ by "stepwise coupling polymerization". In CN1105677, PCT/CN2008/072588, WO2010/034161 A1, it was disclosed that the side groups are phenyl, methyl, ethylene Preparation of regular ladder-PSSQ based on contour. They further studied the preparation of ladder polysiloxanes whose bridging groups are organic groups instead of "-O-", in CN1280995, US Patent US6423772B1 and J.Am.Chem.Soc.2002,124,10482 , Angew.Chem.Int.Ed.2006,45,3112 and Chem.Commun.2009,4079 and other documents reported the preparation of various organic bridging ladder polysiloxanes. These organic bridging groups are connected to the ladder polysilsesquioxane main chain through chemical bonds, such as Si-C, Si-OC, Si-N, etc. In 2013, Cao Xinyu et al. disclosed a siloxane bridging ladder polysiloxane with siloxane as bridging group and siloxane main chain in Chinese patent CN104045831A. RSiX ₃ , R'SiX ₃ and α, ω-silanediol is subjected to the first condensation reaction to form an intermediate; then the intermediate is further subjected to the second condensation and end-capping reaction, and then separated and purified to obtain a ladder polysiloxane with a siloxane bridging group . Because its siloxane bridging group is connected to the silicon atom of the main chain through the -O-(Si) bond, it has better heat resistance than the above-mentioned ladder polysiloxane whose organic bridging group is directly connected to the main chain silicon atom. and molecular chain flexibility. However, the terminal groups of the above trapezoidal polysiloxanes are unstable groups such as hydroxyl or alkoxy groups, and direct application to materials may greatly reduce their thermal stability, or cause side reactions during material modification and curing. Generally, it is necessary to react with an end-capping agent to eliminate the hydroxyl or alkoxy group of the terminal group, increase the stability of the molecule, or further introduce functional groups. However, for siloxane bridging ladder polysiloxanes with strong rigidity or large steric hindrance, it is difficult to achieve a high end-capping rate, or harsh reaction conditions are required, and many unnecessary side reactions are caused.

Cage-shaped polysilsesquioxane (cage-POSS) has a polyhedral structure similar to a cage. So far, there are many types of cage-POSS polyhedrons, and the more common ones are octahedron, decahedron, dodecahedron, etc. [Chem. Rev. 95(5) (1995) 1409; Adv. Mater. 2008, 20, 2970–2976; Chem. Rev. 2010, 110, 2081–2173, PCT/US00/21455]. cage-POSS is also divided into fully condensed or incompletely condensed type. The incompletely condensed cage-POSS has an incomplete or unclosed cage structure. For example, one corner of the cage structure is missing, and the adjacent Si atoms cannot achieve complete Condensation, the presence of silanol or siloxy groups. In order to improve its performance in practical application, for the incompletely condensed cage-POSS, the "capping" method can be used to make the condensation complete and introduce functional groups; in addition, for the completely condensed or incompletely condensed cage-POSS, Both can be copolymerized with other siloxanes or compounds through the reactivity of side groups to derive products with better compatibility or structure [Macromolecules 2007; 40:682–8; Macromolecular Rapid Communications 2009; 30:1015–20] .

It can be seen that although there are many studies on trapezoidal and cage polysiloxanes, most of them focus on the preparation, modification and application of ladder-PSSQ and cage-POSS; Or the ladder polysiloxane of "siloxane bridging group", all still need capping reaction to eliminate unstable groups such as terminal hydroxyl groups of ladder polysiloxane, the process is complicated, and may affect the original ladder polysiloxane performance.

Contents of the invention

For the deficiencies in the prior art, one of the purposes of the present invention is to provide a self-blocking ladder/cage polysiloxane, which combines the advantages of the siloxane bridging ladder polysiloxane, and overcomes the need to use The capping reaction further reduces and eliminates the defects of unstable groups such as terminal hydroxyl groups; in addition, the polysiloxane has higher high temperature resistance and stability, and it is soluble or meltable, and can be conveniently processed , or modify other polymers or silicone materials.

The second object of the present invention is to provide a method for preparing the above self-blocking ladder/cage polysiloxane.

The third object of the present invention is to provide the application of the above-mentioned self-blocking ladder/cage polysiloxane.

The object of the present invention is achieved through the following technical solutions:

A self-blocking ladder polysiloxane, which has a structure shown in the following formula (I):

In formula (I), R, R', A, A' are the same or different, and are independently selected from alkyl, alkenyl, aryl, aryloxy or arylalkoxy; the alkyl is substituted or Unsubstituted, the aryl is substituted or unsubstituted; the substituent is -NR ₁ R ₂ , -SR ₃ , -OR ₄ , halogen or alkenyl; the R ₁ , R ₂ and R ₃ are the same or different, independently selected from H, C _1-10 alkyl or amino-substituted C _1-10 alkyl; said R ₄ is selected from glycidyl ether, acryloyl or α-C _1-4 alkyl acryloyl ;

m is independently 0 or z, but not all 0; said z is an integer of 1-10;

n is an integer of 1-500.

Wherein, the alkyl can be C _1-10 alkyl, preferably C _1-6 alkyl, also preferably C _1-4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, etc.

Wherein, the alkenyl can be C _2-10 alkenyl, preferably C _2-6 alkenyl, such as vinyl, 1-propenyl, 1-butenyl and the like.

Wherein, the aryl group may be a C _6-20 aryl group, preferably a C _6-10 aryl group, such as phenyl, naphthyl and the like.

Wherein, the "aryl" or "alkyl" in the aryloxy or arylalkoxy is as defined above.

Wherein, the substituent may be -NH ₂ , -NH(CH ₂ CH ₂ NH ₂ ), -SH, -OH or -Cl.

Wherein, said R, R', A, A' are the same or different, independently selected from methyl, ethyl, isopropyl, isobutyl, vinyl, allyl, phenyl, glycidyl ether Oxypropyl, methacryloxypropyl, acryloxypropyl, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, mercaptopropyl, chlorobenzene group, phenol group or benzyl alcohol group and other groups.

Wherein, the proportion of repeating units in which m is 0 is less than 50%, preferably less than or equal to 10%.

Wherein, n is 2-100, further may be 3-50, and further may be 4-20.

The present invention also provides a self-blocking clathrate polysiloxane, which has a structure shown in the following formula (II):

In formula (II), R, R', A, A', m and n are as defined above.

The present invention also provides a self-blocking polysiloxane, which comprises a self-blocking ladder polysiloxane (a) of a structure shown in formula (I) and a self-blocking cage polysiloxane of a structure shown in formula (II) (b), and the mole percentage of polysiloxane (a) and polysiloxane (b) is greater than or equal to 50 mol%.

Preferably, the mole percentage of polysiloxane (a) and polysiloxane (b) is greater than or equal to 70 mol%, more preferably greater than or equal to 80 mol%, and more preferably greater than or equal to 90 mol%.

Wherein, the mole percentage of polysiloxane (a) in the sum of polysiloxane (a) and polysiloxane (b) is greater than 0 to less than 100 mol%, such as 1 to 99 mol%, and can also be 5-50mol%.

The present invention also provides a kind of preparation method of above-mentioned self-blocking polysiloxane, it comprises the following steps:

(1) Synthesis of siloxane bridging intermediates, whose raw materials include RSiX ₃ and/or R'SiX ₃ , and HO(AA'SiO) _z H; wherein, R, R', A, A', z The definition is the same as above; X is the same or different, independently selected from OH, Cl, alkoxy (such as C _1-10 alkoxy, specifically methoxy, ethoxy, isopropoxy or isobutoxy) one or more of

(2) hydrolyzing the intermediate;

(3) Condensation in the presence of a basic catalyst to obtain the self-blocked polysiloxane.

Among them, the step (1) is specifically: in the reactor, add RSiX ₃ and/or R'SiX ₃ , then add HO(AA'SiO) _z H, the first organic solvent and the first catalyst to react to obtain the silane oxygen bridge base intermediate.

Preferably, the reaction temperature is -20°C to 60°C; the reaction time is 30 minutes to 10 hours.

Preferably, post-treatment steps are also included after the reaction, specifically neutralization, filtration and/or distillation to obtain a silaneoxy bridging group intermediate solution.

Preferably, the molar ratio of RSiX ₃ to R'SiX ₃ is (0-1):1, or the molar ratio of R'SiX ₃ to RSiX ₃ is (0-1):1.

Preferably, the molar ratio of RSiX ₃ and/or R'SiX ₃ to HO(AA'SiO) _z H is (1.8˜20):1.

Preferably, the amount of the first catalyst used is 0.0001 to 10 times the mole number of HO(AA'SiO) _z H. It is also preferably 0.0001 to 1 times.

Preferably, the first catalyst is selected from one or more of ammonia, pyridine, hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, phosphoric acid, organic amine (ammonium), organic acid, metal organic compound, and ion exchange resin. Also preferably, the first catalyst is selected from one of ammonia and organic amine (ammonium).

Preferably, the first organic solvent in step (1) is selected from: benzene, toluene, xylene, methanol, ethanol, isopropanol, isobutanol, hexane, cyclohexane, acetone, methyl ethyl ketone, tetrahydrofuran, cyclic Hexanone, dioxane, diethyl ether, petroleum ether, acetonitrile, dichloromethane, dichloroethane, tetrachloromethane, chloroform, ethyl acetate, dimethyl sulfoxide, dimethylformamide one or more species.

Wherein, step (2) specifically includes: adding water, a second catalyst and a second organic solvent to the intermediate obtained in step (1), or adding alcohol, a second catalyst and a second organic solvent; hydrolyzing the reaction to obtain a hydrolyzed product.

Preferably, in step (2), the amount of water or alcohol added is 0 to 20 times the molar number of HO(AA'SiO) _z H added in step (1), but not 0; for example 0.0001 to 20 times. The amount of the second catalyst used is 0.0001 to 10 times the mole number of HO(AA'SiO) _z added in step (1).

Preferably, the temperature of the hydrolysis reaction in step (2) is 0° C. to 150° C., and the reaction time is 30 minutes to 10 hours.

Preferably, step (2) further includes a post-processing step after the completion of the hydrolysis reaction, specifically removing water from the reaction mixture and separating it by filtration to obtain a hydrolyzate solution.

Preferably, the second catalyst is selected from one or more of ammonia, pyridine, hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, phosphoric acid, organic amine (ammonium), organic acid, metal organic compound, and ion exchange resin. Also preferably, the second catalyst is selected from one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and organic acids.

Preferably, in step (2), the second organic solvent is selected from the group consisting of: benzene, toluene, xylene, ether, anisole, phenetole, ethyl acetate, tetrahydrofuran, dioxane, chloroform, di One or more of ethyl chloride. This is because on the one hand, these solvents form an azeotropic system with water, which can distill a small amount of moisture at a lower temperature; on the other hand, the subsequent condensation reaction needs to be carried out in a weakly polar or even nonpolar environment, making The terminal hydroxyl groups can be effectively condensed to reduce branching and crosslinking.

Wherein, in the step (3), the azeotropic dehydration condensation is carried out by solvent in the presence of a basic catalyst.

Wherein, the step (3) specifically includes: adding a basic catalyst to the hydrolyzate solution obtained in the step (2) to carry out a condensation reaction, and continuously steaming out the water produced by the condensation reaction during the reaction process; obtaining the self-blocked polysilicon oxane.

The water produced by the condensation reaction is continuously distilled out during the reaction of step (3), which is a method of azeotropic removal of water through the solvent, and the water generated in the condensation reaction is removed through the azeotropic solvent and water, so that the reaction proceeds forward.

Preferably, in step (3), the amount of the basic catalyst used is 0.0001 to 10 times the mole number of HO(AA'SiO) _z added in step (1). The basic catalyst is selected from one or more of metal hydroxides or hydrates thereof, metal organic compounds, and organic amines (ammonium).

Preferably, in step (3), the condensation reaction temperature is 0-40° C. above the azeotropic point of the solvent and water, and the reaction time is 30 minutes to 48 hours.

Preferably, in step (3), after the condensation reaction is completed, a post-processing step is also included, specifically neutralizing, removing water, filtering, separating and purifying the mixture obtained from the condensation reaction to obtain the self-blocked polysiloxane.

In above-mentioned first catalyzer, second catalyzer or basic catalyst, described organic acid is preferably one or more in formic acid, acetic acid, oxalic acid, citric acid, trifluoroacetic acid; Described organic amine (ammonium ) is preferably one or more of triethylamine, trihydroxyethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; the metal The organic compound is selected from sodium methoxide, sodium ethoxide, dibutyltin dilaurate, dioctyltin dilaurate, dialkyldiaryltin, butyl titanate, ethyl titanate, tetraethoxyzirconium, tetrapropylene One or more of zirconium oxide, tetrabutoxy zirconium, and tetraisopropoxy zirconium; the ion exchange resin is selected from quaternary ammonium ion exchange resins based on styrene divinylbenzene copolymers, benzene One or more of sulfonic acid ion exchange resins based on ethylene divinylbenzene copolymers, carboxylic acid ion exchange resins based on styrene divinylbenzene copolymers, and carboxylic acid ion exchange resins based on polyacrylic acid species; the metal hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and barium hydroxide.

Polysiloxane (a), polysiloxane (b) and/or self-blocking polysiloxane of the present invention can be used for the improvement of properties such as temperature resistance, radiation resistance and weather aging resistance of organic coating macromolecule; And It can improve the heat resistance, refractive index, adhesion, air tightness and mechanical properties of high-power light-emitting diode (LED) packaging adhesives and silicone pressure-sensitive adhesives, such as: strength, modulus, hardness, etc.

Wherein, the organic coating polymer is, for example, hydroxyl-terminated silicone oil, hydroxyl resin, resin curable by hydrosilylation, polyurethane resin, epoxy resin, acrylic resin, alkyd resin and the like. The packaging glue or silicone pressure-sensitive adhesive includes silicone resin.

The present invention also provides a modified polymer material for coatings, the raw materials of which include polysiloxane (a), polysiloxane (b) and/or self-blocked polysiloxane of the present invention.

Wherein, the polymer material is, for example, hydroxyl-terminated silicone oil, hydroxyl resin, resin curable by hydrosilylation, polyurethane resin, epoxy resin, acrylic resin, alkyd resin, and the like.

The present invention also provides a packaging glue or silicone pressure-sensitive adhesive, which includes a modified silicone resin, and the raw materials of the modified silicone resin include polysiloxane (a) and polysiloxane of the present invention. alkane (b) and/or self-blocking polysiloxane.

The beneficial effects of the present invention are:

The polysiloxane of the present invention has higher high temperature resistance (such as the temperature of 5% weight loss under nitrogen atmosphere is greater than 430 ℃, preferably greater than 450 ℃, also preferably greater than 460 ℃) and light transmittance (such as light transmittance greater than 90%; the refractive index is 1.500-1.600, preferably 1.520-1.560), and has solubility and meltability. When mixed with other materials, it will not bring side reactions due to end groups.

The polysiloxane of the present invention can be used for the improvement of properties such as temperature resistance, radiation resistance and weather aging resistance of organic coating macromolecules; and can improve the heat resistance of high-power light-emitting diode (LED) packaging glue and organic silicon pressure-sensitive adhesive Sex, refractive index, cohesiveness, air tightness and mechanical properties, such as: strength, modulus, hardness, etc.

Description of drawings

Fig. 1. FTIR spectrogram of the product obtained in Example 1 of the present invention.

Fig. 2. XRD spectrogram of the product obtained in Example 1 of the present invention.

detailed description

As described above, the present invention provides a self-blocking ladder polysiloxane, a self-blocking clathrate polysiloxane and a self-blocking polysiloxane, which refers to a self-blocking agent and condensation A soluble polysiloxane having a three-dimensional trapezoidal or cage molecular structure that is higher than the known siloxane bridging ladder polysiloxane or cage polysiloxane.

The present invention innovatively discloses a self-blocking ladder/cage polysiloxane and a self-blocking polysiloxane, which combines the advantages of the existing siloxane bridging ladder polysiloxane, and at the same time It also overcomes the need to use end-capping reactions to reduce or eliminate unstable groups such as terminal hydroxyl groups.

The degree of condensation in the present invention is calculated by following formula:

Degree of condensation formula In D _x or T _x , x represents the number of Si atoms connected to other Si atoms by Si-O-(Si) bonds, and D represents T is for R is a side group.

Calculated by the formula, the degree of condensation of the self-blocking trapezoidal/cage polysiloxane of the present invention is significantly higher than that of the original siloxane bridging ladder polysiloxane, and the terminal group is significantly reduced, without The capping reaction is carried out, which reduces the reaction procedure and the occurrence of side reactions. The polysiloxane of the present invention has higher high temperature resistance and stability, and has solubility and meltability, and when mixed with other materials, it will not bring about side reactions due to end groups. It can be used to modify semiconductor materials, packaging materials, medical materials, etc., to improve their thermal stability, processability, and adjust the refractive index.

Example 1

Preparation of Cage and Ladder Self-Blocking Polysiloxanes via Vinyltrimethoxysilane, Diphenylsilanediol.

(1) Under the protection of dry nitrogen, 30.7 grams (0.21 moles) of vinyltrimethoxysilane were placed in a multi-necked flask equipped with a condenser tube and a dropping funnel, and 30 grams of tetrahydrofuran was mixed with Add 10.3 grams (0.05 moles) of diphenylsilanediol mixture dropwise into a multi-neck flask, and feed ammonia gas at the same time; after 4 hours, stop feeding ammonia gas, and gradually raise the temperature to 70°C for 1 hour to remove Remove ammonia; after stopping the reaction, distill to remove part of tetrahydrofuran, methanol and unreacted vinyltrimethoxysilane to obtain an intermediate solution with a concentration of about 30%;

(2) At 40°C, the intermediate solution obtained in step (1) with a concentration of about 30% is mixed with 7.2 grams (0.40 moles) of water and 0.044 grams (4.00×10 ^-4 moles of HCl) hydrochloric acid, and mixed at 40°C Reaction for 4 hours; the mixture obtained from the reaction is separated by removing water and filtering to obtain the precursor of the self-capped product;

(3) Add 0.0043 grams of potassium hydroxide (7.68×10 ^-5 moles) to the precursor obtained in step (2), react at 65°C for 4 hours and then heat up to 90°C to distill tetrahydrofuran and water; The mixture is neutralized, dehydrated, filtered, separated and purified to obtain self-blocking polysiloxane (referred to as P1), and said P1 includes caged self-blocking polysiloxane shown in general formula (II) and general formula (I ) shows a ladder-shaped self-blocking polysiloxane, wherein R=R'=vinyl, A=A'=phenyl, m=1. The yield of P1 obtained was 75%.

The obtained P1 is soluble in toluene, FTIR is shown in Figure 1, and XRD spectrum is shown in Figure 2; in the ²⁹ Si-NMR spectrum, there are peaks around -48.4ppm and -81.6ppm, according to the ratio of each peak The degree of condensation was calculated to be 97.3%. The average degree of polymerization n of the product was 7 according to the VPO (vapor pressure osmometer) test.

The polysiloxane of the present invention has excellent optical properties, the transmittance of the P1 in the visible light band is higher than 93%, and the refractive index is 1.547.

The polysiloxane of the present invention also has excellent heat resistance. According to the TGA results, the temperature at which the P1 loses 5% of its weight in a nitrogen atmosphere is 480°C.

Example 2

Cage and ladder self-blocking polysiloxanes were prepared by methacryloxypropyltrimethoxysilane, methyltrimethoxysilane and HO( _{Ph2SiO )} 2H.

(1) Under the protection of dry nitrogen, put 24.8 grams (0.10 moles) of methacryloxypropyl trimethoxysilane and 13.6 grams (0.10 moles) of methyltrimethoxysilane, and a mixture of 36 grams of toluene and dioxane and 20.7 grams (0.05 moles) of HO(Ph ₂ SiO) ₂ H was added dropwise to the multi-neck flask at -20°C. Add 0.002 g (8×10 ^-4 moles) tetrabutylammonium hydroxide at the same time; after dropping for 10 hours, stop the reaction, wash with water until neutral, dry and filter, distill to remove toluene, dioxane, methanol, unreacted methacryloxypropyltrimethoxysilane and unreacted methyltrimethoxysilane yielded pure intermediates;

(2) The intermediate obtained in step (1) is mixed with tetrahydrofuran to obtain an intermediate solution with a concentration of about 40 wt %; at 0° C., the intermediate solution is mixed with 9.0 grams (0.50 moles) of water and 0.05 grams (5.00× 10 ⁻⁴ mol) sulfuric acid mixed, and reacted at 0° C. for 3 hours; the reaction mixture was dewatered, filtered and separated to obtain the precursor of the self-capped product;

(3) Add 1.42 grams (0.005 moles) of barium hydroxide (Ba(OH) ₂ 8H ₂ O) to the precursor obtained in step (2), react at 40°C for 4 hours, then heat up to 90°C to distill Tetrahydrofuran and water; the reaction mixture is neutralized, dewatered, filtered, separated and purified to obtain self-blocking polysiloxane (referred to as P2), and the P2 includes caged self-blocking polysiloxane represented by general formula (II) Oxane and ladder-shaped self-blocking polysiloxane represented by general formula (I), wherein R=methacryloxypropyl, R'=methyl, A=A'=phenyl, m=2. The yield of P2 obtained was 70%.

It can be seen from the FTIR spectrum that absorption peaks appear at 1071cm ^-1 , 1130cm ^-1 , 1262cm ^-1 , 1429cm ^-1 , 2843cm ^-1 and 2940cm ^-1 . From the ¹ H-NMR spectrum, it can be seen that peaks appear at 7.7 ppm, 7.4 ppm, 5.6 ppm, 4.1 ppm, 3.4 ppm and 0.6 ppm. The molecular weight was analyzed by VPO (vapor pressure osmometer) test, and the average value of n was 7. Soluble in tetrahydrofuran. The degree of condensation is 96.7%.

The polysiloxane of the present invention has excellent optical properties, the transmittance of the P2 in the visible light band is higher than 93%, and the refractive index is 1.550.

The polysiloxane of the present invention also has excellent heat resistance. According to the TGA results, the temperature at which the P2 loses 5% of its weight in a nitrogen atmosphere is 471°C.

Example 3

Cage and ladder self-blocking polysiloxanes were prepared by phenyltrichlorosilane, methyltrichlorosilane and HO(MePhSiO) _3H .

(1) Under the protection of dry nitrogen, in a multi-necked flask equipped with a condenser tube and a dropping funnel, put 10.6 grams (0.05 moles) of phenyltrichlorosilane and 14.9 grams (0.10 moles) of methyltrichlorosilane Mix, add 60 g of tetrahydrofuran and dichloroethane and 41.3 g (0.08 moles) of HO(MePhSiO) ₃ H into the multi-neck flask dropwise at 0°C, and add 80.8 g (0.8 moles) of triethylamine at the same time After 20 hours of dropwise addition, the reaction was stopped, washed with water to neutrality, dried and filtered, and distilled to remove tetrahydrofuran, dichloroethane, unreacted phenyltrichlorosilane and unreacted methyltrichlorosilane to obtain pure Intermediate;

(2) The intermediate obtained in step (1) is mixed with dichloromethane to obtain an intermediate solution with a concentration of about 40% by weight; at -10°C, the intermediate solution is mixed with 14.4 grams (0.80 moles) of water and 0.0005 grams (8.00×10 ^-6 mol) nitric acid was mixed and reacted at -10°C for 5 hours; the reaction mixture was dewatered and filtered to obtain the precursor of the self-capped product;

(3) Add 0.005 grams (8.00×10 ^-5 moles) of sodium ethylate to the precursor obtained in step (2), react at 0°C for 2 hours and then heat up to 50°C to distill dichloromethane and water; The resulting mixture is neutralized, dehydrated, separated by filtration and purified to obtain self-blocking polysiloxane (referred to as P3), said P3 comprising caged self-blocking polysiloxane shown in general formula (II) and general formula ( I) The ladder-shaped self-blocking polysiloxane shown, wherein R=phenyl, R'=methyl, A=methyl, A'=phenyl, m=3. The yield of P3 obtained was 83%.

It can be seen from the FTIR spectrum that absorption peaks appear at 1070cm ^-1 , 1120cm ^-1 , 1430cm ^-1 , 1601cm ^-1 , 2942cm ^-1 and 3380cm ^-1 . Soluble in acetone or tetrahydrofuran. The molecular weight was analyzed by VPO (vapor pressure osmometer) test, and the average value of n was 8. The degree of condensation is 97.5%.

The polysiloxane of the present invention has excellent optical properties, the transmittance of the P3 in the visible light band is higher than 91%, and the refractive index is 1.543.

The polysiloxane of the present invention also has excellent heat resistance. According to the TGA results, the temperature at which the P3 loses 5% of its weight in a nitrogen atmosphere is 469°C.

Example 4

Cage and ladder self-blocking polysiloxanes prepared from vinyltrimethoxysilane, aminopropyltrimethoxysilane and diphenylsilanediol.

(1) Under the protection of dry nitrogen, put 29.6 grams (0.20 moles) of vinyl trimethoxysilane and 10.8 grams (0.06 moles) of aminopropyl trimethyl Oxysilane, add 40 grams of ethanol and acetone and 20.7 grams (0.05 moles) of diphenylsilanediol to the multi-neck flask dropwise at 10 ° C, while adding 22.8 grams (0.25 moles) of tetramethylhydrogen Ammonium oxide; after adding dropwise for 1 hour, stop the reaction, wash with water until neutral, dry and filter, distill to remove ethanol, acetone, methanol, unreacted vinyltrimethoxysilane and unreacted aminopropyltrimethoxy Silanes give pure intermediates;

(2) the intermediate obtained in step (1) is mixed with carbon tetrachloride to obtain an intermediate solution with a concentration of about 30wt%; at 20°C, the intermediate solution with a concentration of about 30wt% is mixed with 1.0 grams (1.00 mol) of water and 19.2 grams (0.4 mol) of formic acid were mixed and reacted at 30° C. for 4 hours; the reaction mixture was separated by removing water and filtering to obtain the precursor of the self-blocking product;

(3) Add 2.58 grams (0.01 moles) of tetrabutylammonium hydroxide to the precursor obtained in step (2), react at 40°C for 4 hours and then heat up to 85°C to distill carbon tetrachloride and water; The mixture is neutralized, dehydrated, filtered, separated and purified to obtain self-blocking polysiloxane (referred to as P4), and said P4 includes caged self-blocking polysiloxane shown in general formula (II) and general formula (I ), where R=vinyl, R'=aminopropyl, A=A'=phenyl, m=1. The yield of P4 obtained was 74%.

It can be seen from the FTIR spectrum that absorption peaks appear at 1070cm ^-1 , 1120cm ^-1 , 1430cm ^-1 , 1601cm ^-1 , 2942cm ^-1 and 3380cm ^-1 . It can be seen from the XRD spectrum that there are obvious peaks at the positions of 2θ of 8.5° and 19.5°. The molecular weight was analyzed by VPO (vapor pressure osmometer) test, and the average value of n was 7. Soluble in xylene. The degree of condensation is 94.9%.

The polysiloxane of the present invention has excellent optical properties, the transmittance of the P4 in the visible light band is higher than 90%, and the refractive index is 1.544.

The polysiloxane of the present invention also has excellent heat resistance. According to the TGA results, the temperature at which the P4 loses 5% of its weight in a nitrogen atmosphere is 477°C.

Example 5

Cage and trapezoidal self-blocking polysiloxanes were prepared by glycidoxypropyltrimethoxysilane and HO( _{Me2SiO )} 5H.

(1) Under the protection of dry nitrogen, in the multi-necked bottle equipped with condenser tube and dropping funnel, put 47.2 grams (0.20 mole) of glycidyl etheroxypropyl trimethoxysilane at 60 ℃. The mixed solution of 25 grams of benzene and cyclohexane and 7.76 grams (0.02 moles) of HO(Me ₂ SiO) ₅ H was added dropwise in the multi-neck flask, and ammonia gas was passed into it simultaneously; after 1 hour of dropwise addition, the ammonia gas flow was stopped, Gradually raise the temperature to 70°C for 1 hour to remove ammonia, distill to remove benzene, cyclohexane, methanol and unreacted glycidyloxypropyltrimethoxysilane to obtain a pure intermediate;

(2) the intermediate obtained in step (1) is mixed with toluene and ether to obtain an intermediate solution with a concentration of about 1 wt %; at 30° C., the intermediate solution is mixed with 7.2 grams (0.40 moles) of water and 0.044 grams ( 4.00×10 ^-4 moles of HCl) hydrochloric acid were mixed and reacted at 30° C. for 1 hour; the reaction mixture was dewatered and filtered to obtain the precursor of the self-capped product;

(3) Add 0.006 g (1×10 ^-5 mol) of dibutyltin dilaurate to the precursor obtained in step (2), react at -20°C for 40 hours, then heat up to 90°C to distill out toluene and ether and water; the resulting reaction mixture is neutralized, dewatered, filtered, separated and purified to obtain self-blocking polysiloxane (referred to as P5), and said P5 includes caged self-blocking polysiloxane shown in general formula (II) alkane and a ladder-shaped self-blocking polysiloxane represented by general formula (I), wherein R=R'=glycidyloxypropyl, A=phenyl, A'=phenyl, m=5. The yield of P5 obtained was 88%.

It can be seen from the FTIR spectrum that absorption peaks appear at 1068cm ^-1 , 1121cm ^-1 , 1429cm ^-1 , 1601cm ^-1 , 2842cm ^-1 and 3080cm ^-1 . It can be seen from the XRD spectrum that there are obvious peaks at the positions of 2θ of 8.0° and 19.1°. The molecular weight was analyzed by VPO (vapor pressure osmometer) test, and the average value of n was 6. Soluble in petroleum ether. The degree of condensation was 94.3%.

The polysiloxane of the present invention has excellent optical properties, the transmittance of the P5 in the visible light band is higher than 90%, and the refractive index is 1.539

The polysiloxane of the present invention also has excellent heat resistance. According to the TGA results, the temperature at which the P5 loses 5% of its weight in a nitrogen atmosphere is 479°C.

Example 6

Preparation of Cage and Ladder Self-Blocking Polysiloxanes from Phenyltrichlorosilane, 3-Acryloyloxytrichlorosilane and Diphenylsilanediol.

(1) Under the protection of dry nitrogen, put 21.2 grams (0.10 moles) of phenyltrichlorosilane and 24.8 grams (0.10 moles) of 3-acryloyloxy Base trichlorosilane mixed, at 30 ° C, the mixture of 75 grams of xylene and petroleum ether and 21.6 grams (0.10 moles) of diphenylsilanediol was added dropwise to the multi-necked bottle, while adding 151.5 grams (1.5 moles) Triethylamine; after 48 hours of dropping, stop the reaction, wash with water until neutral, dry and filter, distill to remove xylene, petroleum ether, unreacted phenyltrichlorosilane and unreacted 3-acryloyloxy Trichlorosilane gives pure intermediate;

(2) the intermediate obtained in step (1) is mixed with ethyl acetate to obtain an intermediate solution with a concentration of about 65 wt %; at 0° C., the intermediate solution is mixed with 14.4 grams (0.80 moles) of water and 1.80 grams ( 0.30 moles) of acetic acid were mixed and reacted at -20°C for 25 hours; the reaction mixture was dewatered and filtered to obtain the precursor of the self-capped product;

(3) Add 51 grams (0.15 moles) of butyl titanate to the precursor obtained in step (2), react at 60°C for 15 hours and then heat up to 75°C to distill off ethyl acetate and water; After neutralization, water removal, separation and purification by filtration, self-blocking polysiloxane (referred to as P6) is obtained, and said P6 includes caged self-blocking polysiloxane shown in general formula (II) and general formula (I) The ladder-shaped self-blocking polysiloxane is shown, wherein R=phenyl, R'=3-acryloyloxytrichlorosilane, A=A'=phenyl, m=1. The yield of P6 obtained was 79%.

It can be seen from the FTIR spectrum that absorption peaks appear at 1069cm ^-1 , 1130cm ^-1 , 1261cm ^-1 , 1429cm ^-1 , 2842cm ^-1 and 3010cm ^-1 . From the ¹ H-NMR spectrum, it can be seen that peaks appear at 7.8 ppm, 7.4 ppm, 5.4 ppm, 4.0 ppm, 3.3 ppm and 0.3 ppm. The molecular weight was analyzed by VPO (vapor pressure osmometer) test, and the average value of n was 8. Soluble in petroleum ether. The degree of condensation is 95.7%.

The polysiloxane of the present invention has excellent optical properties, the transmittance of the P6 in the visible light band is higher than 95%, and the refractive index is 1.556.

The polysiloxane of the present invention also has excellent heat resistance. According to the TGA results, the temperature at which the P6 loses 5% of its weight in a nitrogen atmosphere is 469°C.

Example 7

Cage and trapezoidal self-blocking polysiloxanes were prepared by aminopropyltrimethoxysilane and HO(MePhSiO ₎ 5H.

(1) Under the protection of dry nitrogen, in a multi-necked flask equipped with a condenser tube and a dropping funnel, 35.8 grams (0.20 moles) of aminopropyltrimethoxysilane were placed, and 115 grams of tetrahydrofuran and Add the mixture of isobutanol and 34.9 g (0.05 moles) of diphenylsilanediol dropwise into a multi-neck flask, and feed ammonia gas at the same time; after 35 hours of dropping, stop feeding ammonia gas, and gradually raise the temperature to 70°C for reaction 2 hours to remove ammonia, distillation to remove THF, isobutanol, methanol and unreacted aminopropyltrimethoxysilane to give pure intermediate;

(2) The intermediate obtained in step (1) is mixed with trichloroethane to obtain an intermediate solution with a concentration of about 15 wt %; at 110° C., the intermediate solution is mixed with 9.0 grams (0.50 moles) of water and 0.05 grams of (5.00×10 ^-4 mol) sulfuric acid was mixed and reacted at 110° C. for 30 minutes; the reaction mixture was dewatered and filtered to obtain the precursor of the self-capped product;

(3) Add 5.7 grams (0.10 moles) of calcium hydroxide to the precursor obtained in step (2), react at 110°C for 6 hours and then heat up to 150°C to distill trichloroethane and water; After neutralization, water removal, separation and purification by filtration, self-blocking polysiloxane (referred to as P7) is obtained, and said P7 includes caged self-blocking polysiloxane shown in general formula (II) and general formula (I) Ladder-shaped self-blocking polysiloxane shown, where R=R'=aminopropyl, A=methyl, A'=phenyl, m=5. The yield of P7 obtained was 77%.

It can be seen from the FTIR spectrum that absorption peaks appear at 1072cm ^-1 , 1129cm ^-1 , 1429cm ^-1 , 1595cm ^-1 and 3080cm ^-1 . The degree of condensation is 96.6%. It can be seen from the XRD spectrum that there are obvious peaks at the positions of 2θ of 7.6° and 19.3°. The molecular weight was analyzed by VPO (vapor pressure osmometer) test, and the average value of n was 8. Soluble in benzene and toluene. The degree of condensation is 95.7%.

The polysiloxane of the present invention has excellent optical properties, the transmittance of the P7 in the visible light band is higher than 92%, and the refractive index is 1.539.

The polysiloxane of the present invention also has excellent heat resistance. According to the TGA results, the temperature at which the P7 loses 5% of its weight in a nitrogen atmosphere is 474°C.

Example 8

Cage and ladder self-blocking polysiloxanes prepared from vinyltrimethoxysilane, phenyltrimethoxysilane and diisopropylsilanediol.

(1) Under the protection of dry nitrogen, in a multi-necked flask equipped with a condenser tube and a dropping funnel, put 14.8 grams (0.10 moles) of vinyltrimethoxysilane and 19.8 grams (0.10 moles) of phenyltrimethoxy base silane mixed, at 40 ℃, the mixture of 80 grams of tetrahydrofuran and dioxane and 19.8 grams (0.10 moles) of diisopropylsilanediol was added dropwise to the multi-necked flask, while adding 0.002 grams (8 × 10 ^-4 mol) into tetrabutylammonium hydroxide; dropwise for 5 hours, stop the reaction, wash to neutral, dry and filter, distill to remove tetrahydrofuran, dioxane, methanol, unreacted vinyltrimethoxysilane and unreacted phenyltrimethoxysilane to give a pure intermediate;

(2) The intermediate obtained in step (1) is mixed with tetrahydrofuran to obtain an intermediate solution with a concentration of about 0.5 wt %; at 25° C., the intermediate solution is mixed with 36.0 grams (2.00 moles) of water and 0.96 grams (5.00 ×10 ^-3 mol) citric acid mixed, and reacted at 25°C for 1.5 hours; the reaction mixture was dewatered, filtered and separated to obtain the precursor of the self-capped product;

(3) Add 6.7 grams (0.05 moles) of trihydroxyethylamine to the precursor obtained in step (2), react at 70°C for 30 minutes and then heat up to 75°C to distill THF and water; Neutralization, water removal, filtration separation and purification to obtain self-blocking polysiloxane (referred to as P8), said P8 includes caged self-blocking polysiloxane shown in general formula (II) and general formula (I) shows a ladder-shaped self-blocking polysiloxane, wherein R = vinyl, R' = phenyl, A = A' = isopropyl, m = 1. The yield of P8 obtained was 90%.

It can be seen from the FTIR spectrum that absorption peaks appear at 1012cm ^{-1 , 1072cm -1 , 1129cm -1 , 1429cm -1 , 1595cm -1 and} 3080cm ^-1 . The molecular weight was analyzed by VPO (vapor pressure osmometer) test, and the average value of n was 9. Soluble in cyclohexane. The degree of condensation is 98.2%.

The polysiloxane of the present invention has excellent optical properties, and the transmittance of the P8 in the visible light band is higher than 90%. The refractive index is 1.521.

The polysiloxane of the present invention also has excellent heat resistance. According to the TGA results, the temperature at which the P8 loses 5% of its weight in a nitrogen atmosphere is 470°C.

Example 9

Cage and trapezoidal self-blocking polysiloxanes were prepared by mercaptopropyltrimethoxysilane, phenyltrimethoxysilane and HO( _{Ph2SiO )} 2H.

(1) Under the protection of dry nitrogen, in a multi-necked flask equipped with a condenser tube and a dropping funnel, put 19.6 grams (0.10 moles) of mercaptopropyltrimethoxysilane and 19.8 grams (0.10 moles) of phenyl Trimethoxysilane was mixed, and a mixture of 65 grams of toluene and 41.4 grams (0.10 moles) of HO(Ph ₂ SiO) ₂ H was added dropwise to a multi-neck flask at -20°C, and ammonia gas was introduced at the same time; 10 After 1 hour, the ammonia gas was stopped, and the temperature was gradually raised to 70 ° C for 2 hours to remove ammonia, and distillation was performed to remove toluene, methanol, unreacted mercaptopropyltrimethoxysilane and unreacted phenyltrimethoxysilane to obtain pure intermediate;

(2) The intermediate obtained in step (1) is mixed with trichloroethane to obtain an intermediate solution with a concentration of about 50 wt %; at 60° C., the intermediate solution is mixed with 18.0 grams (1.00 moles) of water and 0.05 grams of (5.00×10 ^-4 mol) sulfuric acid was mixed and reacted at 60°C for 45 minutes; the reaction mixture was dewatered and filtered to obtain the precursor of the self-capped product;

(3) Add 3.68 grams of tetraethylammonium hydroxide (0.025 moles) to the precursor obtained in step (2), react at 60°C for 2 hours and then heat up to 130°C to distill trichloroethane and water; The mixture obtained from the reaction is neutralized, dewatered, filtered, separated and purified to obtain self-blocking polysiloxane (referred to as P9), and said P9 includes caged self-blocking polysiloxane shown in general formula (II) and general formula (I) Ladder-shaped self-blocking polysiloxane, wherein R = mercaptopropyl, R' = phenyl, A = A' = phenyl, m = 2. The yield of P9 obtained was 73%.

It can be seen from the FTIR spectrum that absorption peaks appear at 1070cm ^-1 , 1131cm ^-1 , 1430cm ^-1 , 1599cm ^-1 and 3074cm ^-1 . The degree of condensation is 95.5%. It can be seen from the XRD spectrum that there are obvious peaks at the positions of 2θ of 8.8° and 18.3°. The molecular weight was analyzed by VPO (vapor pressure osmometer) test, and the average value of n was 5. Soluble in dichloroethane. The degree of condensation was 91.3%.

The polysiloxane of the present invention has excellent optical properties, the transmittance of the P9 in the visible light band is higher than 92%, and the refractive index is 1.549.

The polysiloxane of the present invention also has excellent heat resistance. According to the TGA results, the temperature at which the P9 loses 5% of its weight in a nitrogen atmosphere is 488°C.

Example 10

Cage and trapezoidal self-blocking polysiloxanes were prepared by vinyltrichlorosilane, methyltrichlorosilane and HO( _Ph2SiO ) _3H .

(1) Under the protection of dry nitrogen, put 12.9 grams (0.08 moles) of vinyl trichlorosilane and 14.9 grams (0.10 moles) of methyltrimethoxy Silane was mixed, and a mixture of 160 grams of tetrahydrofuran and 55.8 grams (0.09 moles) of HO(Ph ₂ SiO) ₃ H was added dropwise to a multi-neck flask at -20°C, and 109 grams (1.1 moles) of triethylamine was added at the same time; After dropping for 30 hours, the reaction was stopped, washed with water until neutral, dried and filtered, and distilled to remove tetrahydrofuran, unreacted vinyltrichlorosilane and unreacted methyltrichlorosilane to obtain a pure intermediate;

(2) The intermediate obtained in step (1) is mixed with tetrahydrofuran to obtain an intermediate solution with a concentration of about 65 wt %; at -20° C., the intermediate solution is mixed with 28.8 grams (1.60 moles) of water and 4.9 grams (0.05 mol) phosphoric acid mixed and reacted at -20°C for 9 hours; the reaction mixture was dewatered and filtered to obtain the precursor of the self-capped product;

(3) Add 0.2 grams (0.005 moles) of sodium hydroxide to the precursor obtained in step (2), react at 55°C for 1 hour and then heat up to 80°C to distill tetrahydrofuran and water; neutralize the resulting mixture , dewatering, filtration separation and purification, to obtain self-blocking polysiloxane (referred to as P10), said P10 includes cage-shaped self-blocking polysiloxane shown in general formula (II) and trapezoidal polysiloxane shown in general formula (I) Self-blocking polysiloxane, where R=vinyl, R'=methyl, A=A'=phenyl, m=3. The resulting yield of P10 was 70%.

It can be seen from the XRD spectrum that there are obvious peaks at the positions of 2θ of 8.3° and 19.3°. From the ²⁹ Si-NMR spectrum, it can be seen that peaks appear at 47.4 ppm, 65.4 ppm and 80.9 ppm. The molecular weight was analyzed by VPO (vapor pressure osmometer) test, and the average value of n was 8. Soluble in dioxane. The degree of condensation is 97.6%.

The polysiloxane of the present invention has excellent optical properties, the transmittance of the P10 in the visible light band is higher than 90%, and the refractive index is 1.529.

The polysiloxane of the present invention also has excellent heat resistance. According to the TGA results, the temperature at which the P10 loses 5% of its weight in a nitrogen atmosphere is 477°C.

Example 11

Add the P1 obtained in Example 1 to Dow Corning silicone resin products 6630A and 6630B to enhance the performance of the silicone resin

After fully mixing 1 gram of P1 of Example 1, 1 gram of 6630A and 8 grams of 6630B, add 400 ppm of Karstedt catalyst, mix evenly again, pour it into a mold, and after degassing in a vacuum oven, heat up to 150°C and react 6 hours, the modified organosilicon material was obtained.

The refractive index of the material was measured to be 1.564. The transmittance is 92.1% in the wavelength range of visible light. According to thermogravimetric analysis, the temperature at the time of weight loss of 5% was 483°C, and the residual amount after heating up to 750°C was 76%. However, the temperature of the modified organosilicon material made from unblocked polysiloxane is 426° C. when the weight loss is 5%, and the residual amount after heating to 750° C. is 54%.

Example 12

The P2 obtained in Example 2 is added to the commercially available hydroxyl-terminated silicone oil to enhance the performance of the hydroxyl-terminated silicone oil

Add 50 grams of commercially available 107# hydroxyl-terminated silicone oil into the kneader, after dewatering at high temperature (100° C.) and high pressure (1 kPa) for 4 hours, cool down to room temperature, and add 3 grams of P2 obtained in Example 2 and 0.003 gram of chloroplatinic acid catalyst, kneaded for 2 hours, and took out the mixture to obtain a modified hydroxyl-terminated silicone oil.

The mechanical properties were tested according to the method of GB/T14683-2003, the modulus was 0.83MPa, the tensile strength was 1.54MPa, and the elongation at break was 339%. TGA results show that the temperature at the time of weight loss of 5% is 474°C, and the residual amount after heating up to 750°C is 74%. The temperature of the modified hydroxy-terminated silicone oil made from unblocked polysiloxane is 421° C. when the weight loss is 5%, and the residual amount after heating up to 750° C. is 49%.

Claims (10)

1. a self-blocking ladder polysiloxane, characterized in that, the polysiloxane has a structure shown in the following formula (I): In formula (I), R, R', A, A' are the same or different, and are independently selected from alkyl, alkenyl, aryl, aryloxy or arylalkoxy; the alkyl is substituted or Unsubstituted, the aryl is substituted or unsubstituted; the substituent is -NR ₁ R ₂ , -SR ₃ , -OR ₄ , halogen or alkenyl; the R ₁ , R ₂ and R ₃ are the same or different, independently selected from H, C _1-10 alkyl or amino-substituted C _1-10 alkyl; said R ₄ is selected from glycidyl ether, acryloyl or α-C1-4 alkyl acryloyl; m is independently 0 or z, but not all 0; said z is an integer of 1-10; n is an integer of 1-500. 2. self-blocking ladder polysiloxane according to claim 1, is characterized in that, described alkyl can be C _1-10 alkyl, preferred C 1-6 alkyl, also preferably C _1-4 alkyl , such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. Preferably, the alkenyl group may be a _C2-10 alkenyl group, preferably a C2-6 alkenyl group, such as vinyl, 1-propenyl, 1-butenyl and the like. Preferably, the aryl group may be a C6-20 aryl group, preferably a _C6-10 aryl group, such as phenyl, naphthyl and the like. Preferably, the "aryl" or "alkyl" in the aryloxy or arylalkoxy is as defined above. Preferably, the substituent may be -NH ₂ , -NH(CH ₂ CH ₂ NH ₂ ), -SH, -OH or -Cl. Preferably, said R, R', A, A' are the same or different, independently selected from methyl, ethyl, isopropyl, isobutyl, vinyl, allyl, phenyl, glycidol Etheroxypropyl, methacryloxypropyl, acryloxypropyl, aminopropyl, 3-(2-aminoethyl)-aminopropyl, chloropropyl, mercaptopropyl, chloro Groups such as phenyl, phenol or benzyl alcohol. Preferably, the proportion of repeating units in which m is 0 is less than 50%, preferably less than or equal to 10%. Preferably, n is 2-100, further may be 3-50, and may further be 4-20. 3. a self-blocking clathrate polysiloxane, characterized in that, the polysiloxane has a structure shown in the following formula (II): In formula (II), the definition of R, R', A, A', m, n is the same as that in claim 1 or 2. 4. A self-blocking polysiloxane, characterized in that, the polysiloxane comprises the self-blocking trapezoidal polysiloxane (a) described in claim 1 or 2 and the self-blocking cage described in claim 3 polysiloxane (b), and the mole percentage of polysiloxane (a) and polysiloxane (b) is greater than or equal to 50 mol%. Preferably, the molar percentage of polysiloxane (a) and polysiloxane (b) is greater than or equal to 70 mol%, more preferably greater than or equal to 80 mol%, and more preferably greater than or equal to 90 mol%. Preferably, the mole percentage of polysiloxane (a) in the sum of polysiloxane (a) and polysiloxane (b) is greater than 0 to less than 100 mol%, such as 1-99 mol%. 5. a preparation method of the self-blocking polysiloxane of claim 4, is characterized in that, described method comprises the steps: (1) Synthesis of siloxane bridging intermediates, whose raw materials include RSiX ₃ and/or R'SiX ₃ , and HO(AA'SiO) _z H; wherein, R, R', A, A', z The definition is the same as above; X is the same or different, independently selected from OH, Cl, alkoxy (such as C _1-10 alkoxy, specifically methoxy, ethoxy, isopropoxy or isobutoxy) one or more of (2) hydrolyzing the intermediate; (3) Condensation in the presence of a basic catalyst to obtain the self-blocked polysiloxane. 6. The preparation method according to claim 5, characterized in that, step (1) is specifically: in the reactor, add RSiX ₃ and/or R'SiX ₃ , then add HO(AA'SiO) _z H, The first organic solvent and the first catalyst react to obtain a silane oxygen bridge intermediate. Preferably, the reaction temperature is -20°C to 60°C; the reaction time is 30 minutes to 10 hours. Preferably, post-treatment steps are also included after the reaction, specifically neutralization, filtration and/or distillation to obtain a silaneoxy bridging group intermediate solution. Preferably, the molar ratio of RSiX ₃ to R'SiX ₃ is (0-1):1, or the molar ratio of R'SiX ₃ to RSiX ₃ is (0-1):1. Preferably, the molar ratio of RSiX ₃ and/or R'SiX ₃ to HO(AA'SiO) _z H is (1.8˜20):1. Preferably, the amount of the first catalyst used is 0.0001 to 10 times the mole number of HO(AA'SiO) _z H. Preferably, the first catalyst is selected from one or more of ammonia, pyridine, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, organic amine (ammonium), organic acid, metal organic compound, and ion exchange resin. Also preferably, the first catalyst is selected from one of ammonia and organic amine (ammonium). Preferably, the first organic solvent in step (1) is selected from: benzene, toluene, xylene, methanol, ethanol, isopropanol, isobutanol, hexane, cyclohexane, acetone, methyl ethyl ketone, tetrahydrofuran, cyclic Hexanone, dioxane, diethyl ether, petroleum ether, acetonitrile, dichloromethane, dichloroethane, tetrachloromethane, chloroform, ethyl acetate, dimethyl sulfoxide, dimethylformamide one or more species. 7. The preparation method according to claim 5 or 6, characterized in that, step (2) is specifically: adding water, a second catalyst and a second organic solvent to the intermediate obtained in step (1), or adding Alcohol, a second catalyst and a second organic solvent; a hydrolysis reaction to obtain a hydrolyzed product. Preferably, in step (2), the amount of water or alcohol added is 0 to 20 times the molar number of HO(AA'SiO) _z H added in step (1), but not 0; for example 0.0001 to 20 times. The amount of the second catalyst used is 0.0001 to 10 times the mole number of HO(AA'SiO) _z added in step (1). Preferably, the temperature of the hydrolysis reaction in step (2) is 0° C. to 150° C., and the reaction time is 30 minutes to 10 hours. Preferably, step (2) further includes a post-processing step after the completion of the hydrolysis reaction, specifically removing water from the reaction mixture and separating it by filtration to obtain a hydrolyzate solution. Preferably, the second catalyst is selected from one or more of ammonia, pyridine, hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, phosphoric acid, organic amine (ammonium), organic acid, metal organic compound, and ion exchange resin. Also preferably, the second catalyst is selected from one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and organic acids. Preferably, in step (2), the second organic solvent is selected from the group consisting of: benzene, toluene, xylene, ether, anisole, phenetole, ethyl acetate, tetrahydrofuran, dioxane, chloroform, di One or more of ethyl chloride. This is because on the one hand, these solvents form an azeotropic system with water, which can distill a small amount of moisture at a lower temperature; on the other hand, the subsequent condensation reaction needs to be carried out in a weakly polar or even nonpolar environment, making The terminal hydroxyl groups can be effectively condensed to reduce branching and crosslinking. Preferably, in step (3), the solvent is azeotropically dehydrated and condensed in the presence of a basic catalyst. Preferably, the step (3) is specifically: adding a basic catalyst to the hydrolyzate solution obtained in the step (2) to carry out a condensation reaction, and continuously steaming out the water generated by the condensation reaction during the reaction; obtaining the self-blocked poly silicone. Preferably, in step (3), the amount of the basic catalyst used is 0.0001 to 10 times the mole number of HO(AA'SiO) _z added in step (1). The basic catalyst is selected from one or more of metal hydroxides or hydrates thereof, metal organic compounds, and organic amines (ammonium). Preferably, in step (3), the condensation reaction temperature is 0-40° C. above the azeotropic point of the solvent and water, and the reaction time is 30 minutes to 48 hours. Preferably, in step (3), after the condensation reaction is completed, a post-processing step is also included, specifically neutralizing, removing water, filtering, separating and purifying the mixture obtained from the condensation reaction to obtain the self-blocked polysiloxane. Preferably, in the above-mentioned first catalyst, second catalyst or basic catalyst, the organic acid is preferably one or more of formic acid, acetic acid, oxalic acid, citric acid, trifluoroacetic acid; Amine (ammonium) is preferably one or more in triethylamine, trihydroxyethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; The metal organic compound is selected from sodium methylate, sodium ethylate, dibutyltin dilaurate, dioctyltin dilaurate, dialkyldiaryltin, butyl titanate, ethyl titanate, tetraethoxyzirconium , tetrapropoxy zirconium, tetrabutoxy zirconium, tetraisopropoxy zirconium or one or more; the ion exchange resin is selected from quaternary ammonium ion exchange resin based on styrene divinylbenzene copolymer Resin, sulfonic acid ion exchange resin based on styrene divinylbenzene copolymer, carboxylic acid ion exchange resin based on styrene divinylbenzene copolymer, carboxylic acid ion exchange resin based on polyacrylic acid one or more; the metal hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and barium hydroxide. 8. Use of polysiloxane (a) according to claim 1 or 2, polysiloxane (b) according to claim 3 or self-blocking polysiloxane according to claim 4, characterized in that , the polysiloxane can be used to improve the properties of organic coating polymers such as temperature resistance, radiation resistance and weather aging resistance; or, it can improve the resistance of high-power light-emitting diode (LED) encapsulation glue and silicone pressure-sensitive adhesive Thermal properties, refractive index, cohesiveness, air tightness and mechanical properties, such as: strength, modulus, hardness, etc. Preferably, the organic coating polymer is, for example, hydroxyl-terminated silicone oil, hydroxyl resin, resin cured by hydrosilylation, polyurethane resin, epoxy resin, acrylic resin, alkyd resin and the like. Preferably, the packaging glue or silicone pressure-sensitive adhesive includes silicone resin. 9. A modified polymer material for coating, characterized in that, the raw material of the polymer material comprises polysiloxane (a) according to claim 1 or 2, polysiloxane (a) according to claim 3 Oxane (b) or the self-blocking polysiloxane of claim 4. Preferably, the polymer material is, for example, hydroxyl-terminated silicone oil, hydroxyl resin, resin curable by hydrosilylation, polyurethane resin, epoxy resin, acrylic resin, alkyd resin and the like. 10. An encapsulation glue or silicone pressure-sensitive adhesive, characterized in that, the glue comprises a modified silicone resin, and the raw material of the modified silicone resin comprises the polysilicon according to claim 1 or 2. Oxane (a), polysiloxane (b) according to claim 3 or self-blocking polysiloxane according to claim 4 .