CN108250326B - A kind of polymer containing hydroxyl functionalized side group and its preparation method and branched/network polymer - Google Patents

Abstract

The present invention provides a kind of polymer containing hydroxyl functionalized side group and its preparation method and branched/network polymer, and the preparation method of the polymer containing hydroxyl functionalized side group comprises the following steps: (1) under heat or light In the presence of a compound that can generate free radicals under the action, the polymer containing unsaturated double bonds is contacted with an organosilicon compound containing a mercapto functional group to react; (2) the reaction product obtained in step (1) is hydrolyzed to obtain the obtained The polymer containing the hydroxyl functional side group; the structure of the organosilicon compound containing the mercapto functional group is shown in the general formula (II) HS-X-SiY ₃ Y ₄ Y ₅ . The present invention can obtain a branched polymer through the hydrogen bond between the hydroxyl groups in the functional group, so that the mixing uniformity of the polymer containing the hydroxyl-functionalized side group and the filler is greatly improved, and at the same time, the blending of the vulcanized rubber is improved. performance.

Description

A polymer containing hydroxyl-functionalized side groups and its preparation method and branched/network network polymer

technical field

The invention relates to the field of functional polymers, more specifically, to a polymer containing hydroxyl-functionalized side groups, a preparation method thereof, and a branched/network polymer.

Background technique

The practical applications of nonpolar polymers are usually limited by their nonpolar characteristics. The functional modification of side groups in the polymer chain is an important way to improve the performance of polymers and broaden the application fields of polymers. As one of the three major synthetic materials, synthetic rubber can be used to manufacture tires, transmission belts, oil pipelines, wire and cable sheaths, etc., and it needs to be blended with inorganic fillers or organic compounds during use. Therefore, the difference in polarity leads to relatively poor blending properties of polymers and fillers, such as the blending of styrene-butadiene rubber, butadiene rubber or isoprene rubber with carbon black or white carbon black inorganic fillers containing polar groups on the surface. The mixing performance is relatively poor, which affects the quality and performance of the final product. To this end, it is necessary to develop polymers that are polarly functionalized with side groups in the polymer chain, usually prepared by functionalization of side groups. Using the polar functionalized polymer with opposite side groups in the molecular chain, through the interaction of polar groups and the principle of similar compatibility, can improve its blending performance with carbon black or white carbon black, and the filler can play a better role Reinforcing effect.

In addition, the topology of the polymer molecular chain is also one of the important factors affecting its blending properties with fillers. Branched polymers have excellent processability and mechanical properties due to their special molecular chain structure and morphology. For example, long-chain branched polyisoprene with high molecular weight and high cis-1,4 structure content has greatly improved its molecular chain degradation during processing, and the rubber strain crystallization ability and tensile strength have been significantly improved. Performance indicators such as thermal stability, elongation at break, tear strength, hardness and wet skid resistance are significantly improved, and even better than the related properties of natural rubber, see patent documents CN104231120B and CN100365030C. Branched polymers can also improve the mixing uniformity between them and inorganic fillers, and improve the physical and mechanical properties and dynamic mechanical properties of the vulcanizate, see patent documents CN201210332297.2, CN201310251919.3, CN201310180858.6 and CN201310251852.3. Similarly, star-branched butyl rubber and star-branched styrene-butadiene rubber can achieve the unity of improved processing performance, physical and mechanical properties and dynamic mechanical properties, see: Zhao Jinbo, Beijing University of Chemical Technology Master's Thesis, 2008; Liu Xiaojiao, Liu Jiwen, Zhao Shugao. Synthetic Rubber Industry, 2015,38(2):145-149.

Branched polymers mainly have the following synthesis methods: grafting grafting, grafting grafting (chain-end coupling reaction), macromonomer method and molecular chain coupling method. For the preparation of branched butyl rubber, branched styrene-butadiene rubber, branched polybutadiene rubber and branched polyisoprene, it is mainly synthesized by grafting method or intermolecular coupling reaction. Specifically, for the chain end coupling reaction, a branching agent is added when the polymerization system is not terminated, so that the functional group of the branching agent is coupled with the active chain end of the linear molecule. The branching agent is an organic halide, epoxy-containing Amine compounds with amino groups, amino-containing aldehydes or thials, partially epoxidized or anhydride-functionalized unsaturated natural oils, tin tetrachloride, phenyltin trichloride, silicon tetrachloride, functional polymers, etc., but these multifunctional compounds usually need to be added when the active chain of the polymerization reaction exists, the reaction efficiency is relatively low, and because the low molecular weight part with the active end group in the polymerization system is more likely to participate in the coupling reaction, resulting in short chain branching There are relatively many products, see patent documents EP0863165A1, EP1026181A1, EP1099711A2 and EP1650227A2; for the intermolecular coupling method, add bis (multi) functional group compounds (such as S ₂ Cl ₂ , dimercapto alkanes compound) to carry out double bond addition reaction, set up a branched structure through -SS- or -CC-bonding, improve the cold flow resistance of raw rubber, improve the physical and mechanical properties and dynamic mechanical properties of vulcanized rubber, see patent documents US5567784, TW201418298, CN201210332297.2, CN201310251919.3, CN201310180858.6 and CN201310251852.3. In order to improve the relationship between wet skid resistance and rolling resistance, a silane coupling agent structural unit is introduced into the molecular chain of diene polymer or diene and styrene, such as 3-mercaptopropyltrimethoxysilane, see patent literature CN201310512238, CN201310512794, CN201310513369. Structural units are repeatedly linked by covalent bonds to form polymers, see Pan Zuren, Polymer Chemistry (Second Edition), Chemical Industry Press, 1997.

In summary, functionalized or branched polymers in the molecular chain can endow materials with more excellent processing properties and mechanical properties, but there are still some problems in their preparation methods, such as the coupling efficiency of the active chain end coupling reaction. It is relatively low, and there are relatively many short-chain branched products; it is difficult to control the addition reaction of -S-S-bonds, and crosslinking reactions easily occur locally, resulting in gels and affecting rubber properties, and -S-S-bonds are easy to mix during mixing. Breakage occurs. In particular, there are currently no polymers that simultaneously contain side group hydroxyl functionalization, branching, and network structure of the molecular chain.

Contents of the invention

The purpose of the present invention is to address the problems in the prior art, to provide a polymer containing hydroxyl-functionalized side groups and its preparation method, branched/network polymer, through the hydrogen bond between the hydroxyl groups in the functional group, it can By obtaining branched polymers and increasing the degree of branching of molecular chains, the mixing uniformity of polymers containing hydroxyl-functionalized side groups and fillers is greatly improved, and at the same time, the performance of its blended vulcanizate is improved.

The present invention provides a polymer containing hydroxyl-functionalized side groups, the molecular chain side groups of the polymer contain functional groups represented by the general formula (I)-SX-SiY ₁ Y ₂ OH, wherein the general formula (I In ), X is selected from C ₁ -C ₁₅ straight chain or branched chain alkylene, Y ₁ and Y ₂ are the same or different, each independently selected from halogen, hydroxyl or C ₁ -C ₂₀ straight chain or branched chain alkyl .

According to the polymer provided by the present invention, the weight average molecular weight (M _w ) of the polymer is preferably 1.0×10 ⁴ to 1.5×10 ⁶ , more preferably 5.0×10 ⁴ to 1.2×10 ⁶ , further preferably 8.0×10 6 10 ⁴ to 1.0×10 ⁶ ; the functionality of the hydroxyl group in the general formula (I) is preferably 0.008% to 15%, more preferably 0.01% to 10%, and even more preferably 0.03% to 8%.

Preferably, the side groups containing the general formula (I) are randomly distributed on the main chain of the polymer molecule.

The present invention also provides a method for preparing a polymer containing hydroxyl-functionalized side groups, the method comprising the steps of:

(1) In the presence of a compound that can generate free radicals under the action of heat or light, the polymer containing an unsaturated double bond is contacted with an organosilicon compound containing a mercapto functional group to react;

(2) subjecting the reaction product obtained in step (1) to a hydrolysis reaction to obtain the polymer containing hydroxyl-functionalized side groups;

The structure of the organosilicon compound containing a mercapto functional group is shown in the general formula (II) HS-X-SiY ₃ Y ₄ Y ₅ , wherein, in the general formula (II), X is selected from C ₁ -C ₁₅ straight chain or Branched chain alkylene, preferably selected from C ₁ -C ₁₂ straight chain or branched chain alkylene, further preferably selected from C ₁ -C ₁₀ straight chain or branched chain alkylene; Y ₃ , Y ₄ and Y ₅ are the same or Different, Y ₃ is selected from C ₁ -C ₂₀ straight chain or branched chain alkoxy, Y ₄ and Y ₅ are each independently selected from halogen, C ₁ -C ₂₀ straight chain or branched chain alkyl or C ₁ - C ₂₀ straight chain or branched chain alkoxy group, preferably selected from C ₁ -C ₁₉ straight chain or branched chain alkyl group or C ₁ -C ₁₉ straight chain or branched chain alkoxy group, more preferably selected from C ₁ -C ₁₈ straight chain or branched chain alkyl or C ₁ -C ₁₈ straight chain or branched chain alkoxy.

According to the preparation method provided by the present invention, preferably, the polymer containing unsaturated double bonds is selected from conjugated diene homopolymers and/or copolymers thereof, more preferably selected from polybutadiene, polyisoprene ene, butadiene/isoprene binary copolymer, styrene/butadiene binary copolymer, styrene/isoprene binary copolymer, isobutylene/isoprene binary copolymer and butadiene At least one of diene/isoprene/styrene terpolymers.

According to the preparation method provided by the present invention, preferably, the organosilicon compound containing a mercapto functional group is selected from 2-mercaptoethylmethylmethoxyethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercapto Propyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyltributoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxy Silane, 6-mercaptohexyltriethoxysilane, 6-mercaptohexyltripropoxysilane, 10-mercaptodecyltriethoxysilane, 10-mercaptodecyltripropoxysilane, 3-mercaptopropyltriethoxysilane Pentyloxysilane, 3-mercaptopropyltrioctoxysilane, 3-mercaptopropyltrinonoxysilane, 3-mercaptopropyltri(tetradecyloxy)silane, 3-mercaptopropyltetradecyloxysilane Hexadecyloctadecyloxysilane, 3,4-dimercaptobutyltriethoxysilane, mercaptomethyldiethoxymethylsilane, 3-mercaptopropyltrichlorosilane and 3-mercaptopropyldi At least one of methoxymethylsilanes.

According to the preparation method provided by the present invention, preferably, the compound that can generate free radicals under the action of heat or light is selected from azo compounds, organic peroxide compounds, benzoin compounds, benzil compounds , at least one of alkyl (aryl) phenone compounds, acyl phosphorus oxides, benzophenone compounds and thioxanthone compounds.

The azo compound is selected from azobisisobutyronitrile, azoisobutyronitrile, azobisisoheptanonitrile, azobiscyanovaleric acid, dimethyl azobisisobutyrate, azodicarboxylic acid Diethyl ester, diisopropyl azodicarboxylate, dibenzyl azodicarboxylate, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 4,4 '-Azobis(4-cyanovaleryl(p-dimethylamino)aniline), 2,2'-Azobis(N-hydroxymethyl)-2-methyl-propionamide and azodiform At least one of amides; preferably selected from the group consisting of azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate, diisopropyl azodicarboxylate and azodicarbonamide at least one of; further preferably selected from azobisisobutyronitrile and/or azobisisoheptanonitrile.

The organic peroxide compound is selected from at least one of benzoyl peroxide, dibenzoyl peroxide, benzoyl tert-butyl peroxide, acetophenone peroxide and lauryl peroxide; preferably At least one selected from benzoyl peroxide, dibenzoyl peroxide, acetophenone peroxide and lauryl peroxide; further preferably selected from benzoyl peroxide, dibenzoyl peroxide, peroxide At least one of acetophenone and lauryl peroxide.

The benzoin compound is selected from at least one of benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether, preferably selected from benzoin isopropyl ether and/or benzoin butyl ether;

The benzil compound is selected from diphenylethanone and/or α,α-dimethoxy-α-phenylacetophenone, preferably selected from diphenylethanone;

The alkyl (aryl) phenone compound is selected from at least one of α, α-diethoxyacetophenone, α-hydroxyalkylphenone and α-aminoalkylphenone, preferably selected from α , α-diethoxyacetophenone and/or α-hydroxyalkylphenone;

The acylphosphine oxide is selected from aroylphosphine oxide and/or bisbenzoylphenylphosphine oxide, preferably selected from aroylphosphine oxide;

The benzophenone compound is selected from at least one of benzophenone, 2,4-dihydroxybenzophenone and 4,4'-bis(dimethylamino)benzophenone, preferably selected from benzophenones and/or 2,4-dihydroxybenzophenones;

The thioxanthone compound is selected from thiopropoxythioxanthone and/or isopropylthioxanthone, preferably from thiopropoxythioxanthone.

According to the preparation method provided by the present invention, preferably, the molar ratio of the organosilicon compound containing a mercapto functional group to the double bond in the polymer containing an unsaturated double bond is 0.005-20:100, more preferably 0.01-10 : 100, more preferably 0.02 to 8: 100.

Preferably, the molar ratio of the initiator to the organosilicon compound containing a mercapto functional group is 0.03˜5.0:100, more preferably 0.05˜3.0:100, further preferably 0.07˜1.6:100.

According to the preparation method provided by the present invention, in step (1), the reaction is carried out in an inert atmosphere, preferably a nitrogen atmosphere; the reaction temperature is preferably 30-150°C, more preferably 40-110°C, and even more preferably 50-100°C ; The reaction time is preferably 1 min to 35 h, more preferably 2 min to 30 h, and even more preferably 5 min to 25 h. Polymers containing unsaturated double bonds and organosilicon compounds containing mercapto functional groups can be reacted in organic media.

According to the preparation method provided by the present invention, in step (2), the polymer solution can be hydrolyzed in an aqueous medium. Preferably, the reaction temperature is 20-100°C, more preferably 30-100°C, further preferably 40-100°C; the reaction time is 1min-10h, more preferably 5min-10h, further preferably 10min-5h.

According to the preparation method provided by the present invention, preferably, in step (2), the pH value of the aqueous medium is 6.5-10.0, more preferably 6.5-9.5, even more preferably 6.5-10.0. Usually, the selected aqueous phase medium is tap water, and the pH value of the tap water used is 6.55.

According to the preparation method provided by the present invention, preferably, in step (2), the volume ratio of the polymer solution to the water phase is 0.1 to 100:100; more preferably 0.5 to 80:100; still more preferably 1 to 50: 100.

According to the preparation method provided by the present invention, in step (1) and step (2), the organic medium is selected from C ₄ -C ₈ alkanes, C ₅ -C ₈ cycloalkanes, C ₆ -C ₁₀ substituted or At least one of unsubstituted aromatic hydrocarbons, raffinate (C ₆ ~C ₈ alkane mixed solution) and halogenated hydrocarbons; preferably selected from pentane, hexane, methylcyclopentane, cyclohexane, heptane , octane, methylcyclohexane, benzene, toluene, xylene, trimethylbenzene, ethylbenzene, dichloromethane, chloroform, dichloroethane, trichloroethane, chloropropane, chlorobutane, chloropentyl One or more of alkanes, chlorobenzenes, and dichlorobenzenes.

According to the preparation method provided by the present invention, in step (1) and step (2), the concentration of the polymer containing unsaturated double bonds in the organic medium is related to molecular weight, organic solvent, temperature, solution viscosity and other factors. According to the preparation method provided by the present invention, preferably, in the polymer/organic medium solution system containing unsaturated double bonds, the concentration of the polymer containing unsaturated double bonds is 10 g/L to 250 g/L, preferably 15 g /L to 220g/L, more preferably 20g/L to 200g/L.

The polymer/organic medium solution system containing unsaturated double bonds can be obtained by dissolving a commercially available conjugated diene polymer in an organic medium, or can be directly obtained by monomer polymerization. The polymerization method includes free Radical polymerization, anionic polymerization, cationic polymerization and coordination polymerization can be carried out batchwise or continuously.

The present invention also provides a polymer containing hydroxyl-functionalized side groups obtained by the above-mentioned preparation method.

The present invention also provides a branched/network polymer. The branched/network polymer is prepared by curing the polymer containing hydroxyl-functionalized side groups to obtain the branched/network polymer. polymer.

According to the branched/network polymer provided by the present invention, the curing treatment may be to remove the solvent from the polymer solution containing hydroxyl functionalized side groups obtained after the hydrolysis reaction, and the solvent removal treatment adopts the method in the art conventional means can be achieved.

In the present invention, in the presence of a compound capable of generating free radicals under the action of heat or light, the polymer containing unsaturated double bonds performs an efficient click chemical reaction with the organosilicon compound containing a mercapto functional group, and the organosilicon compound containing a mercapto functional group The compound is connected to the macromolecular chain of the conjugated diene polymer, and the reaction efficiency can reach 100%. After the hydrolysis reaction, the polymer containing the hydroxyl-functionalized side group is prepared, and it is further cured to contain the hydroxyl-functionalized side group. In polymers with side groups, part of the hydroxyl groups act as connection points through hydrogen bonds between macromolecular chains to form branched polymers with different degrees of branching. When the functionalization degree of hydroxyl groups is high, the number of hydrogen bonds between macromolecular chains increases , the branching degree of the formed branched polymer increases, and even forms a network polymer, which is insoluble in solvents, can improve and improve the mixing uniformity of polymers and fillers, and improve the performance of organic/inorganic composite materials. If a network polymer that is physically cross-linked by hydrogen bonding is formed, chemical cross-linking is not required, and the physical and mechanical properties of the material can be improved. During processing, when the temperature rises, the hydrogen bond in the branched or networked polymer is weakened or even untied, which not only improves the processing performance, but also has a stronger interaction with the inorganic filler, and improves the mixing of the polymer and the inorganic filler. Effect.

The degree of branching of the branched polymer is represented by a branching factor (g'), for a linear polymer, g'=1.0; for a branched polymer, g'<1.0, the smaller the g' value, the polymer The higher the degree of branching. The formed network polymer can be expressed by the gel content, the higher the gel content, the higher the network polymer content.

Preferably, the degree of branching (g') of the branched polymer of the present invention is 0.45-0.99.

The beneficial effects brought by the technical solution of the present invention are: (1) through the hydroxyl functional modification of the polar side group in the polymer molecular chain and the hydrogen bonding of the hydroxyl group, it can be reversible through non-covalent bonding. Produce a branched chain structure or a network structure, the process is simple, and the branched chain structure or network structure depends on the degree of hydroxyl functionalization; (2) the polymer containing hydroxyl functionalized side groups of the present invention can improve inorganic nanofillers (such as: white Carbon black, etc.) particles in the rubber matrix can reduce or even inhibit the agglomeration of inorganic nano-fillers in the rubber matrix, and at the same time increase the crosslinking density of the blended vulcanized rubber, improve the performance of the vulcanized rubber, reduce rolling resistance, and increase the rigidity of the rubber .

Description of drawings

Fig. 1 is a phase contrast microscope photo of the polymer containing hydroxyl functionalized side groups described in Example 10 of the present invention blended with silica equivalent to 10% of the mass of the polymer.

Detailed ways

Preferred embodiments of the present invention will be described in more detail below. While the following examples illustrate preferred embodiments of the invention, it should be understood that the invention can be embodied in various forms and should not be limited by the embodiments set forth herein.

The present invention calculates the microstructure of the polymer through FTIR spectroscopy; by combining a multi-angle light scattering detector (MALLS) with a conventional SEC/RI and viscosity (Viscometer) detector system, the weight-average molecular weight ( _Mw ) of the polymer is tested , number average molecular weight (M _n ), molecular weight distribution (M _w /M _n ) and branching factor (g'), wherein g' is the ratio of the intrinsic viscosity of branched polymers and linear polymers with the same molecular weight. The dispersion state of silica in rubber was characterized by phase contrast microscopy (PCM). Standard SH/T 1050-2014 is used to test the gel content. The cross-link density was measured by low-field NMR cross-link density method.

Taking polybutadiene rubber as an example, the formula of vulcanized rubber (refer to the national standard GB/T8660-2008, without adding carbon black, process oil, zinc oxide and stearic acid): 100 parts by mass of rubber, 1.5 parts by mass of sulfur S, Accelerator TBBS 0.9 parts by mass, white carbon black 10 parts by mass, and the vulcanization condition is 145° C.×30 min.

The dynamic mechanical properties of the vulcanized rubber were tested with a TA-Q800DMA dynamic mechanical analyzer, the temperature range was -130°C to 100°C, and the heating rate was 10°C/min. The tanδ value of the vulcanized rubber at 60°C can represent the heat generation or rolling resistance of the rubber, the smaller the value, the better; the storage modulus E' at room temperature 25°C represents the rigidity of the material, the larger the value, the higher the rigidity, It is also shown that the handling performance of the tire is improved when used as a tire material.

Example 1

Under a nitrogen atmosphere, the linear high cis polybutadiene (cis content = 98.3%) was dissolved in hexane (concentration 60g/L), and the polymer solution was mixed with azobisisobutyronitrile and mercaptopropane After mixing triethoxysilane, react at 103°C for 30 minutes, wherein the molar ratio of triethoxysilane to polymer is 0.04:100, and azobisisobutyronitrile to propyl The molar ratio of triethoxysilane is 0.1:100. After the reaction, the polymer solution was hydrolyzed at 100° C. for 1 hour, and the pH of the aqueous phase was 9.9. After removal of hexane, a polymer containing hydroxyl-functionalized side groups was prepared. The polymer containing hydroxyl-functionalized side groups forms branched polybutadiene through hydrogen bonding between molecular chains, wherein: the cis-1,4 structure content is 98.3%, and the weight average molecular weight (M _w ) is 3.4× 10 ⁵ , the molecular weight distribution index (M _w /M _n ) is 3.2, and the branching factor (g') is 0.94.

The polybutadiene containing hydroxyl-functionalized side groups and the silicon dioxide equivalent to 10% of the mass of the polymer can achieve a uniform mixing effect, which is beyond the reach of ordinary polybutadiene.

In the case of adding 10% white carbon black by weight, the crosslink density test was carried out on the vulcanizate, and the crosslink density was 21.0×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested: the tanδ value at 60°C was 0.084, and the storage modulus (E') at 25°C was 4.0MPa. Compared with Comparative Example 1, the crosslinking density increased by 408%; the tanδ value at 60°C decreased by 70%, the heat generation decreased, and the rolling resistance decreased; improved handling performance.

Example 2

The experimental method is the same as in Example 1, except that the molar ratio of mercaptopropyltriethoxysilane to polymer double bonds is 0.2:100, and the molar ratio of azobisisobutyronitrile to mercaptopropyltriethoxysilane The ratio is 1.6:100, and the pH value of the water phase in the hydrolysis reaction is 6.55. Polybutadiene containing hydroxyl-functionalized side groups and corresponding branched polybutadiene were prepared, wherein: cis-1,4 structure content was 98.3%, M _w was 3.2×10 ⁵ , and M _w /M _n was 2.4, g' is 0.95.

Polybutadiene containing hydroxyl-functional side groups can be evenly mixed with silicon dioxide equivalent to 10% of the mass of the polymer, which is beyond the reach of ordinary polybutadiene.

Adding 10% white carbon black by weight, the crosslinking density of the vulcanizate was tested, and the crosslinking density was 24.3×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested: the tanδ value at 60°C was 0.12, and the storage modulus (E') at 25°C was 3.8MPa. Compared with Comparative Example 1, the crosslink density increased by 488%; the tanδ value at 60°C decreased by 57%, the heat generation decreased, and the rolling resistance decreased; the storage modulus (E') increased by 189%, and the rigidity increased.

Example 3

The experimental method is the same as in Example 1, except that the molar ratio of mercaptopropyltriethoxysilane to polymer double bonds is 0.04:100, and the molar ratio of azobisisobutyronitrile to mercaptopropyltriethoxysilane The ratio is 0.1:100, react at 103°C for 180 minutes, and the hydrolysis reaction time is 3.5h. Polybutadiene containing hydroxyl-functionalized side groups and corresponding branched polybutadiene were prepared, wherein: cis-1,4 structure content was 98.3%, M _w was 3.8×10 ⁵ , and M _w /M _n was 2.1, g' is 0.95.

The polybutadiene/hexane solution (4wt%) containing hydroxyl-functionalized pendant groups can be uniformly mixed with silicon dioxide equivalent to 10% of the mass of the polymer, which is beyond the reach of ordinary polybutadiene.

Adding 10% white carbon black by weight, the crosslinking density of the vulcanizate was tested, and the crosslinking density was 32.4×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested: the tanδ value at 60°C was 0.16, and the storage modulus (E') at 25°C was 3.0MPa. Compared with Comparative Example 1, the crosslink density increased by 685%; at 60°C The tan delta value was reduced by 42%, with reduced heat generation and rolling resistance; the storage modulus (E') was increased by 128%, indicating increased stiffness.

Example 4

The experimental method is the same as that of Example 1, except that the polymer solution (98 g/L) was reacted at 103° C. for 120 minutes. Polybutadiene containing hydroxyl-functionalized side groups and corresponding branched polybutadiene were prepared, wherein: cis-1,4 structure content was 98.3%, M _w was 3.9×10 ⁵ , and M _w /M _n was 2.8, g' is 0.95.

Polybutadiene containing hydroxyl-functional side groups can be evenly mixed with silicon dioxide equivalent to 10% of the mass of the polymer, which is beyond the reach of ordinary polybutadiene.

Adding 10% white carbon black by weight, the crosslinking density of the vulcanizate was tested, and the crosslinking density was 21.5×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested: the crosslink density increased by 421%; the tanδ value at 60°C was 0.096, and the storage modulus (E') at 25°C was 3.0MPa. Compared with Comparative Example 1, the tanδ value at 60°C is reduced by 65%, the heat generation is reduced, and the rolling resistance is reduced; the storage modulus (E') is increased by 126%, indicating that the rigidity is improved.

Example 5

The experimental method is the same as in Example 1, except that the concentration of the hexane solution of polybutadiene is 77g/L, and the mol ratio of mercaptopropylmethyldimethoxysilane to the double bond of the polymer is 0.02:100, even The molar ratio of azodiisobutyronitrile to mercaptopropylmethyldimethoxysilane is 0.1:100, and the reaction is carried out at 103°C for 120 minutes. Polybutadiene containing hydroxyl-functionalized side groups and corresponding branched polybutadiene were prepared, wherein: cis-1,4 structure content was 98.3%, M _w was 3.4×10 ⁵ , and M _w /M _n was 2.1, g' is 0.94.

The polybutadiene/hexane solution (6wt%) containing hydroxyl-functionalized side groups can be uniformly mixed with nano-silica equivalent to 10% of the mass of the polymer, which is beyond the reach of ordinary polybutadiene.

Adding 10% white carbon black by weight, the crosslinking density of the vulcanizate was tested, and the crosslinking density was 13.1×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested: the tanδ value at 60°C was 0.19, and the storage modulus (E') at 25°C was 2.3MPa. Compared with Comparative Example 1, the crosslink density increased by 217%; the tanδ value at 60°C decreased by 31%, and the heat generation decreased; the storage elastic modulus (E') increased by 79%, indicating that the rigidity was improved.

Example 6

The experimental method is the same as in Example 1, except that the linear butyl rubber (the molar content of isoprene units is 1.7%) is dissolved in hexane solution (concentration is 50g/L), mercaptopropyltriethoxy The molar ratio of silane to polymer double bond is 3.5:100, the molar ratio of azobisisobutyronitrile to mercaptopropyltriethoxysilane is 0.1:100, and react at 103°C for 40 minutes. The butyl rubber containing hydroxyl-functionalized side groups and the corresponding branched butyl rubber were obtained, wherein: M _w was 4.4×10 ⁵ , M _w /M _n was 2.0, and the branching factor (g') was 0.98.

The polymer/hexane solution (6wt%) containing hydroxyl-functionalized side groups can be uniformly mixed with silicon dioxide equivalent to 10% of the polymer mass, which is beyond the reach of ordinary butyl rubber.

The mass ratio of 10% white carbon black was added to test the crosslink density of the vulcanized rubber, and the crosslink density was 13.5×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested: the tanδ value at 60°C was 0.025, and the storage modulus (E') at 25°C was 1.13MPa. Compared with Comparative Example 2, the crosslink density increased by 32%; the tanδ value at 60°C decreased by 40%, and the heat generation decreased; the storage elastic modulus (E') increased by 28%, indicating that the rigidity was improved.

Example 7

The experimental method of step (1) is the same as in Example 1, except that linear isoprene rubber (cis-1, 4 content is 96.4%) is dissolved in hexane solution (concentration is 50g/L), mercaptopropane The molar ratio of triethoxysilane to polymer double bond is 0.16:100, the molar ratio of azobisisobutyronitrile to mercaptopropyltriethoxysilane is 0.1:100, and react at 103°C for 40 minutes. The experimental method of step (2) is with embodiment 2. The isoprene rubber containing hydroxyl-functionalized side groups and the corresponding branched isoprene rubber are prepared, wherein: the cis-1,4 structure content of the branched isoprene rubber is 96.4%, M _w is 5.0×10 ⁵ , M _w /M _n was 1.7, and the branching factor (g') was 0.99.

The polymer containing hydroxyl-functionalized side groups can be evenly mixed with silica equivalent to 10% of the mass of the polymer, which is beyond the reach of ordinary isoprene rubber.

Adding 10% white carbon black by weight, the crosslinking density of the vulcanizate was tested, and the crosslinking density was 8.5×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested: the tanδ value at 60°C was 0.082, and the storage modulus (E') at 25°C was 1.59MPa. Compared with Comparative Example 3, the crosslink density increased by 12%; the tanδ value decreased by 3%, and the heat generation decreased; the storage elastic modulus (E') increased by 43%, indicating that the rigidity was improved.

Example 8

The experimental method is the same as in Example 1, the difference being that linear styrene-butadiene rubber (styrene mass content is 7.8%) is dissolved in cyclohexane solution (concentration is 50g/L), mercaptopropyltriethoxysilane and The molar ratio of polymer double bonds is 2:100, and the molar ratio of azobisisoheptanonitrile to mercaptopropyltriethoxysilane is 0.1:100. React at 103°C for 40 minutes. The styrene-butadiene rubber containing hydroxyl-functionalized side groups and the corresponding branched styrene-butadiene rubber were obtained, wherein: M _w was 7.6×10 ⁵ , M _w /M _n was 1.8, and the branching factor (g') was 0.73.

The polymer containing hydroxyl-functionalized side groups can be evenly mixed with silicon dioxide equivalent to 10% of the mass of the polymer, which is beyond the reach of ordinary styrene-butadiene rubber.

Adding 10% of white carbon black by weight, the crosslinking density of the vulcanizate was tested, and the crosslinking density was 5.2×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested: the tanδ value at 60°C was 0.040, and the storage modulus (E') at 25°C was 5.5MPa. Compared with Comparative Example 4, the crosslink density increased by 6%; the tanδ value decreased by 5%, the heat generation decreased, and the rolling resistance decreased; the storage modulus (E') increased by 111%, indicating that the rigidity was improved.

Example 9

The experimental method is the same as in Example 1, and the difference is that the mol ratio of mercaptopropyltrimethoxysilane to polymer double bonds is 0.04:100, and the mol ratio of azobisisobutyronitrile to mercaptopropyltrimethoxysilane is 0.1:100, react at 103°C for 120 minutes, the pH value of the aqueous phase in the hydrolysis reaction is 8.01, and the time is 75 minutes. Polybutadiene containing hydroxyl-functionalized side groups and corresponding branched polybutadiene were obtained, wherein: cis-1,4 structure content was 98.3%, M _w was 5.0×10 ⁵ , and M _w /M _n was 2.2, the branching factor (g') is 0.65.

Polymers containing hydroxyl-functional side groups can be evenly mixed with silicon dioxide equivalent to 10% of the mass of the polymer, which is beyond the reach of ordinary polybutadiene.

Adding 10% white carbon black by weight, the crosslinking density of the vulcanizate was tested, and the crosslinking density was 15.4×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested: the tanδ value at 60°C was 0.14, and the storage modulus (E') at 25°C was 6.0MPa. Compared with Comparative Example 1, the crosslink density increased by 273%; the tanδ value at 60°C decreased by 48%, and the heat generation decreased; the storage elastic modulus (E') increased by 361%, indicating that the rigidity was improved.

Example 10

The experimental method is the same as in Example 1, except that the molar ratio of mercaptopropyltriethoxysilane to polymer double bonds is 0.024:100, and the molar ratio of azobisisobutyronitrile to mercaptopropyltriethoxysilane The ratio is 0.1:100, reacted at 103°C for 120 minutes, and the polybutadiene containing hydroxyl-functionalized side groups and the corresponding branched polybutadiene are prepared, in which: the cis-1,4 structure content is 98.3%, M _w was 3.3×10 ⁵ , M _w /M _n was 1.8, and g' was 0.99.

The polymer containing hydroxyl-functionalized side groups can be evenly mixed with silicon dioxide equivalent to 10% of the mass of the polymer. The dispersion effect is shown in Figure 1, which is beyond the reach of ordinary polybutadiene.

Adding 10% white carbon black by weight, the crosslinking density test was carried out on the vulcanizate, and the crosslinking density was 31×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested: the tanδ value at 60°C was 0.094, and the storage modulus (E') at 25°C was 3.7MPa. Compared with Comparative Example 1, the crosslink density increased by 651%; the tanδ value decreased by 66%, the heat generation decreased, and the rolling resistance decreased; the storage modulus (E') increased by 185%, indicating that the rigidity was improved.

Example 11

The experimental method is the same as in Example 1, except that the molar ratio of mercaptopropylmethyldimethoxysilane to polymer double bonds is 0.04:100, and azobisisobutyronitrile to mercaptopropylmethyldiethoxy The molar ratio of base silane was 0.1:100, and the reaction was carried out at 103°C for 120 minutes. After the reaction, the polymer solution was coagulated in water (PH=6.55) at 100°C to remove the solvent, and at the same time, the hydrolysis reaction was carried out for 30 minutes to obtain polybutadiene containing hydroxyl-functionalized side groups and corresponding branched polybutadiene. Polybutadiene, wherein: 98.4%, M _w is 4.0×10 ⁵ , M _w /M _n is 2.3, and g' is 0.93.

Polymers containing hydroxyl-functional side groups can be evenly mixed with silicon dioxide equivalent to 10% of the mass of the polymer, which is beyond the reach of ordinary polybutadiene.

Adding 10% white carbon black by weight, the crosslinking density of the vulcanizate was tested, and the crosslinking density was 17.7×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested, and the tanδ value at 60°C was 0.062, and the storage modulus (E') at 25°C was 2.5MPa. Compared with Comparative Example 1, the crosslink density increased by 329%; the tanδ value decreased by 78%. Improved heat generation and reduced rolling resistance; E' increased by 91%, indicating increased stiffness.

Example 12

The difference between the experimental method and Example 11 is that step (1) was reacted at 103° C. for 90 minutes; the pH value of the water phase in the hydrolysis reaction was 9.9, and the time was 20 minutes. Polybutadiene containing hydroxyl-functionalized side groups and corresponding branched polybutadiene were prepared, wherein: cis-1,4 structure content was 98.4%, M _w was 4.6×10 ⁵ , and M _w /M _n was 4.7, g' is 0.96.

Polymers containing hydroxyl-functional side groups can be evenly mixed with silicon dioxide equivalent to 10% of the mass of the polymer, which is beyond the reach of ordinary polybutadiene.

10% white carbon black was added in mass proportion, and the crosslinking density test was carried out on the vulcanized rubber, and the crosslinking density was 4.6×10 ^-5 mol/cm ³ . The dynamic mechanical properties of the vulcanized rubber were tested, and the tanδ value at 60°C was 0.24, and the storage modulus (E') at 25°C was 1.8MPa. Compared with Comparative Example 1, the crosslink density increased by 11%; the tanδ value decreased by 11%, the heat generation performance was improved, and the rolling resistance was reduced; E' increased by 38%, indicating that the rigidity was improved.

Example 13

The polybutadiene raw material and experimental method are the same as in Example 1, except that the molar ratio of mercaptopropyltrimethoxysilane to polymer double bonds is 0.4:100, azobisisobutyronitrile and mercaptopropyltrimethoxy The molar ratio of base silane was 1:100, and the reaction was carried out at 103°C for 40 minutes. After the reaction, the polymer solution was coagulated in water (PH=6.55) at 100° C. to remove the solvent, and at the same time, hydrolyzed for 60 minutes to obtain a polymer containing hydroxyl-functionalized side groups. Through hydrogen bonding, a network polybutadiene with a high degree of branching is formed, and the content of the network polybutadiene is 85.7%, forming a physical cross-linked network.

10% white carbon black was added in mass proportion, and the dynamic mechanical properties of raw rubber were tested, and the tanδ value at 60°C was 0.23, and the storage modulus (E') at 25°C was 5.13MPa. Compared with Comparative Example 1, the tanδ value at 60°C was reduced by 17%. Improved heat build-up, with a 292% increase in E' at 25°C, indicating increased rigidity.

Example 14

The polybutadiene raw material and experimental method are the same as in Example 1, except that the molar ratio of mercaptopropyltrimethoxysilane to polymer double bonds is 7.2:100, and azobisisobutyronitrile and mercaptopropyltrimethoxy The molar ratio of base silane was 0.056:100, and the reaction was carried out at 103°C for 40 minutes. After the reaction, the polymer solution was hydrolyzed and coagulated to remove the solvent in water (PH=6.55) at 100° C. for 60 minutes. Polybutadiene containing hydroxyl-functionalized side groups and corresponding network polybutadiene with high degree of branching are obtained, wherein: the content of insoluble network polybutadiene is 99.5%, forming a physical cross-linked network.

10% white carbon black was added in mass proportion, and the dynamic mechanical properties of raw rubber were tested, and the tanδ value at 60°C was 0.18, and the storage modulus (E') at 25°C was 5.3MPa. Compared with Comparative Example 1, the tanδ value at 60°C is reduced by 36%, which improves the heat generation performance and reduces the rolling resistance; at 25°C, E' increases by 302%, indicating that the rigidity is improved.

Comparative example 1

Linear high cis polybutadiene (M _w =3.4×10 ⁵ ), the content of cis-1,4 structure is 98.3%. The unfunctionalized polymer/hexane solution (concentration: 60 g/L) was mixed with silicon dioxide equivalent to 10% of the mass of the polymer, and the silicon dioxide was obviously agglomerated and dispersed unevenly. The vulcanizate was tested, and its crosslink density was 4.13×10 ^-5 mol/mL, its tanδ value at 60°C was 0.27, and its storage modulus (E') at 25°C was 1.3MPa.

Comparative example 2

The linear butyl rubber solution described in Example 6 was mixed with silicon dioxide corresponding to 10% of the mass of the polymer, and the silicon dioxide was obviously agglomerated and dispersed unevenly. The vulcanized rubber was tested, and its crosslink density was 10.2×10 ^{- 5} mol/mL, its tanδ value at 60°C was 0.042, and its storage modulus (E') at 25°C was 0.88MPa.

Comparative example 3

The linear isoprene rubber solution described in Example 7 was mixed with silicon dioxide corresponding to 10% of the mass of the polymer, and the silicon dioxide was obviously agglomerated and dispersed unevenly. The vulcanizate was tested, and the crosslink density was 7.6×10 ^{- 5} mol/mL, the tanδ value at 60°C was 0.084, and the storage modulus (E') at 25°C was 1.11MPa.

Comparative example 4

The linear styrene-butadiene rubber solution described in Example 8 was mixed with silicon dioxide equivalent to 10% of the mass of the polymer, and the silicon dioxide was obviously agglomerated and dispersed unevenly. The vulcanizate was tested, and the crosslink density was 4.9×10 ^{- 5} mol/mL, the tanδ value at 60°C was 0.042, and the storage modulus (E') at 25°C was 2.62MPa.

Having described various embodiments of the present invention, the foregoing description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and alterations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (19)

1. a kind of polymer containing hydroxy-functional side group, which is characterized in that contain general formula in the side group of the polymer (I)-S-X-SiY₁Y₂Functional group shown in OH, wherein X is selected from C in logical formula (I)₁-C₁₅Linear chain or branched chain alkylene, Y₁And Y₂ It is identical or different, it is each independently selected from halogen, hydroxyl or C₁-C₂₀Linear or branched alkyl group, it is described to contain hydroxyl-functional The polymer for changing side group is made by the reactive organic silicon compound of polymer and thiohydroxy-containing group containing unsaturated double-bond, described Polymer containing unsaturated double-bond is selected from conjugated diolefin homopolymerization object and/or its copolymer.

2. the polymer according to claim 1 containing hydroxy-functional side group, which is characterized in that the weight of the polymer Average molecular weight is 1.0 × 10⁴~1.5 × 10⁶；The degree of functionality of hydroxyl is 0.008%~15% in logical formula (I).

3. the polymer according to claim 2 containing hydroxy-functional side group, which is characterized in that the weight of the polymer Average molecular weight is 5.0 × 10⁴~1.2 × 10⁶。

4. the polymer according to claim 3 containing hydroxy-functional side group, which is characterized in that the weight of the polymer Average molecular weight is 8.0 × 10⁴~1.0 × 10⁶。

5. the polymer according to claim 2 containing hydroxy-functional side group, which is characterized in that hydroxyl in logical formula (I) Degree of functionality be 0.01%~10%.

6. the polymer according to claim 5 containing hydroxy-functional side group, which is characterized in that hydroxyl in logical formula (I) Degree of functionality be 0.03%~8%.

7. a kind of preparation method of the polymer containing hydroxy-functional side group, which is characterized in that this method comprises the following steps:

(1) in the presence of the compound that can be generated free radicals under heat or light action, by the polymer containing unsaturated double-bond and contain mercapto The organo-silicon compound contact of base functional group is reacted；

(2) reaction is hydrolyzed in the reaction product that step (1) obtains, obtains the polymerization containing hydroxy-functional side group Object；

Such as logical formula (II) HS-X-SiY of the structure of the organo-silicon compound of the thiohydroxy-containing group₃Y₄Y₅It is shown, wherein general formula (II) X is selected from C in₁-C₁₅Linear chain or branched chain alkylene, Y₃、Y₄And Y₅It is identical or different, Y₃Selected from C₁-C₂₀Linear chain or branched chain Alkoxy, Y₄And Y₅It is each independently selected from halogen, C₁-C₂₀Linear or branched alkyl group or C₁-C₂₀Linear chain or branched chain alcoxyl Base.

8. preparation method according to claim 7, wherein the polymer containing unsaturated double-bond is selected from conjugated diene Homopolymer and/or its copolymer.

9. preparation method according to claim 8, wherein the polymer containing unsaturated double-bond be selected from polybutadiene, Polyisoprene, butadiene/isoprene bipolymer, phenylethylene/butadiene bipolymer, styrene/isoprene In bipolymer, isobutene/isoprene bipolymer and butadiene/isoprene/styrene terpolymer extremely Few one kind.

10. preparation method according to claim 7, wherein the organo-silicon compound of the thiohydroxy-containing group are selected from 2- Mercapto ethyl-methyl methoxy-ethoxy-silane, 3- mercaptopropyl trimethoxysilane, 3- mercaptopropyltriethoxysilane, 3- mercapto propyl Tripropoxy silane, three butoxy silane of 3- mercapto propyl, 4- mercapto butyl triethoxysilane, 4- mercapto butyl tripropoxy silane, 6- mercapto hexyl triethoxysilane, 6- mercapto hexyl tripropoxy silane, 10- mercapto ruthenium triethoxysilane, 10- mercapto decyl 3 third Oxysilane, three amoxy silane of 3- mercapto propyl, three octyloxy silane of 3- mercapto propyl, three nonyl epoxide silane of 3- mercapto propyl, 3- mercapto Propyl three (14 oxygroup) silane, 16 oxygroup of 3- mercapto 14 oxygroup of propyl, 18 oxysilane, bis- mercapto butyl of 3,4-, three ethoxy In base silane, thiopurine methyltransferase diethoxymethylsilane, 3- mercapto propyltrichlorosilan and 3- mercapto dimethylamine oxygroup methyl-monosilane It is at least one.

11. preparation method according to claim 7, wherein the compound that can be generated free radicals under the heat or light action, Selected from azo compound, organic peroxide class compound, benzoin class compound, benzil class compound, alkyl phenones Class compound and/or aryl benzene ketone compounds, acyl group phosphorous oxides, benzophenone compound and thioxanthones compound At least one of；

The azo compound be selected from azodiisobutyronitrile, azo isobutyronitrile, azobisisoheptonitrile, azo dicyano valeric acid, Azo-bis-iso-dimethyl, diethyl azodiformate, diisopropyl azodiformate, azoformic acid dibenzyl ester, 2,2 '- Azo bis- (4- methoxyl group -2,4- methyl pentane nitriles), 4,4 '-azos two (4- cyano valeryl (p- dimethylamino) aniline), 2, 2 '-azos bis- (N- methylol) at least one of -2- methyl-malonamics and azodicarbonamide；

The organic peroxide class compound is selected from benzoyl peroxide, dibenzoyl peroxide, the tertiary fourth of benzoyl peroxide At least one of ester, benzoyl peroxide ethyl ketone and dilauroyl peroxide；

The benzoin class compound is in benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether At least one；

The benzil class compound is selected from diphenylethan and/or α, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone；

The alkylbenzene ketone compounds and/or aryl benzene ketone compounds are selected from α, α-diethoxy acetophenone, alpha-hydroxyalkyl At least one of benzophenone and α-amine alkyl phenones；

The acyl group phosphorous oxides is selected from aroyl phosphine oxide and/or bis(benzoylphenyl) phosphine oxide；

The benzophenone compound is selected from benzophenone, 2,4 dihydroxyl benzophenone and bis- (dimethylaminos) two of 4,4'- At least one of benzene (first) ketone；

The thioxanthones compound is selected from thio propoxyl group thioxanthone and/or isopropyl thioxanthone.

12. preparation method according to claim 11, wherein

The azo compound is selected from azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, azo diformazan At least one of sour diisopropyl ester and azodicarbonamide；

The organic peroxide class compound is selected from benzoyl peroxide, dibenzoyl peroxide, benzoyl peroxide ethyl ketone and mistake Aoxidize at least one of lauroyl；

The benzoin class compound is selected from benzoin isopropyl ether and/or benzoin isobutyl ether；

The benzil class compound is selected from diphenylethan；

The alkylbenzene ketone compounds and/or aryl benzene ketone compounds are selected from α, α-diethoxy acetophenone and/or α-hydroxyl Alkyl phenones；

The acyl group phosphorous oxides is selected from aroyl phosphine oxide；

The benzophenone compound is selected from benzophenone and/or 2,4 dihydroxyl benzophenone；

The thioxanthones compound is selected from thio propoxyl group thioxanthone.

13. preparation method according to claim 12, wherein

The azo compound is selected from azodiisobutyronitrile and/or azobisisoheptonitrile；

The organic peroxide class compound is selected from benzoyl peroxide, dibenzoyl peroxide, benzoyl peroxide ethyl ketone and mistake Aoxidize at least one of lauroyl.

14. preparation method according to claim 7, wherein the organo-silicon compound of the thiohydroxy-containing group with it is described The molar ratio of double bond is 0.005~20:100 in polymer containing unsaturated double-bond.

15. preparation method according to claim 14, wherein the organo-silicon compound of the thiohydroxy-containing group with it is described The molar ratio of double bond is 0.01~10:100 in polymer containing unsaturated double-bond.

16. preparation method according to claim 15, wherein the organo-silicon compound of the thiohydroxy-containing group with it is described The molar ratio of double bond is 0.02~8:100 in polymer containing unsaturated double-bond.

17. preparation method according to claim 7, wherein in step (1), reaction temperature is 30~150 DEG C, when reaction Between be 1min~35h；In step (2), reaction temperature is 20~100 DEG C, and the reaction time is 1min~10h.

18. being obtained using the preparation method as described in any one of claim 7-17 poly- containing hydroxy-functional side group Close object.

19. a kind of branching/network polymer, which is characterized in that the branching/network polymer is made by the following method: will Polymer described in claim 18 containing hydroxy-functional side group carries out curing process, obtains the branching/network polymer.