Hydroxyl-containing chlorosulfonated polyolefin

Abstract

To provide a chlorosulfonated polyolefin that allows for low-temperature crosslinking.SOLUTION: A hydroxy group-containing chlorosulfonated polyolefin contains chlorine, a chlorosulfone group and a hydroxy group in a polyolefin skeleton.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a hydroxyl-containing chlorosulfonated polyolefin. [Background technology]

[0002] Chlorosulfonated polyolefins have excellent mechanical properties, heat resistance, abrasion resistance, chemical resistance, and bright color, and are therefore used in a variety of applications, such as hose covering materials, electric wire coating materials, packings, gaskets, rolls, escalator handrails, etc. Chlorosulfonated polyolefins are also used as adhesives, coating agents, paints, etc. by dissolving or dispersing them in solvents or water.

[0003] However, crosslinking of chlorosulfonated polyolefins usually requires high temperatures of 140°C or higher, so when used as a coating or paint, the substrate must be heat resistant to temperatures of 140°C or higher, which limits its use.

[0004] Patent Document 1 describes that chlorosulfonated polyethylene paint exhibits abrasion resistance and weather resistance when dried at 100°C for 15 minutes, but does not describe tensile properties.

[0005] Patent Document 2 proposes the use of an organic peroxide with a one-hour half-life temperature of 120°C or less as a crosslinking agent for ethylene-propylene rubber, ethylene-propylene-diene rubber, acrylonitrile-butadiene rubber, and hydrogenated acrylonitrile-butadiene rubber. Although crosslinking at low temperatures is possible by adjusting the half-life temperature of the organic peroxide, there are limitations to its use because organic peroxides cannot crosslink in air.

[0006] Chlorosulfonated polyolefins have excellent mechanical properties, heat resistance, abrasion resistance, chemical resistance, and bright color. However, their applications are limited because crosslinking requires high temperatures of over 140°C. Therefore, there was a demand for chlorosulfonated polyolefins that could be crosslinked at low temperatures. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2-74339 [Patent Document 2] Patent No. 5268313 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above-mentioned problems, and aims to provide a hydroxyl group-containing chlorosulfonated polyolefin that can be crosslinked at low temperatures. [Means for solving the problem]

[0009] As a result of extensive research into solving the above-mentioned problems, the present inventors have found that the hydroxyl group-containing chlorosulfonated polyolefin of the present invention can solve the above-mentioned problems. That is, the respective aspects of the present invention are [1] to

[11] shown below.

[0010] [1] A hydroxyl group-containing chlorosulfonated polyolefin having chlorine, chlorosulfonic acid groups, and hydroxyl groups in the polyolefin skeleton.

[0011] [2] The hydroxyl group-containing chlorosulfonated polyolefin according to [1], wherein the chlorine content is 20 to 50% by weight.

[0012] [3] The hydroxyl group-containing chlorosulfonated polyolefin according to [1] or [2], wherein the content of sulfur derived from the chlorosulfone group is 0.1 to 3% by weight.

[0013] [4] The hydroxyl group-containing chlorosulfonated polyolefin according to any one of [1] to [3], wherein the hydroxyl group content is 3 to 100 mmol / 100 g.

[0014] [5] The hydroxyl group-containing chlorosulfonated polyolefin according to any one of [1] to [4], which has a number average molecular weight of 10,000 to 150,000.

[0015] [6] The hydroxyl group-containing chlorosulfonated polyolefin according to any one of [1] to [5], wherein the polyolefin skeleton further contains an acetoxy group.

[0016] [7] The hydroxyl group-containing chlorosulfonated polyolefin according to [6], wherein the acetoxy group content is 300 mmol / 100 g or less.

[0017] [8] A urethane-forming composition comprising a hydroxyl group-containing chlorosulfonated chlorinated polyolefin according to any one of [1] to [7] and a polyisocyanate.

[0018] [9] A polyurethane that is a cured product of the urethane-forming composition described in [8].

[0019]

[10] A paint containing the polyurethane described in [9].

[0020]

[11] A coating comprising the polyurethane according to [9]. [Effects of the Invention]

[0021] The hydroxyl group-containing chlorosulfonated polyolefin, which is one embodiment of the present invention, can be crosslinked at a lower temperature than conventionally known chlorosulfonated polyolefins, and can be coated onto materials with low heat resistance, which was previously difficult to achieve, to obtain a crosslinked coating. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present invention will be described in detail below.

[0023] The hydroxyl group-containing chlorosulfonated polyolefin according to one embodiment of the present invention is a hydroxyl group-containing chlorosulfonated polyolefin having chlorine, chlorosulfonic groups, and hydroxyl groups in the polyolefin backbone. To achieve excellent flexibility and strength, the chlorine content is preferably 20 to 50 wt%, more preferably 25 to 45 wt%. The sulfur content derived from chlorosulfonic groups is preferably 0.1 to 3 wt%, more preferably 0.5 to 2 wt%. To achieve excellent metal adhesion, the sulfur content is preferably 0.1 wt% or more, more preferably 0.5 wt% or more. From the viewpoint of processability, the sulfur content is preferably 3 wt% or less, more preferably 2 wt% or less. To achieve both excellent flexibility and mechanical properties, the hydroxyl group content is preferably 3 to 100 mmol / 100 g, more preferably 5 to 70 mmol / 100 g. To achieve both excellent mechanical properties and processability, the number average molecular weight is preferably 10,000 to 150,000, more preferably 30,000 to 100,000. The number average molecular weight refers to a value (polystyrene equivalent) measured by gel permeation chromatography (hereinafter abbreviated as GPC).

[0024] The polyolefin skeleton of the hydroxyl group-containing chlorosulfonated polyolefin may contain acetoxy groups. To obtain good color stability, the acetoxy group content is preferably 300 mmol / 100 g or less, and more preferably 200 mmol / 100 g or less.

[0025] The method for synthesizing the hydroxyl group-containing chlorosulfonated polyolefin is not particularly limited, and examples thereof include a method in which a chlorosulfonated ethylene-vinyl acetate copolymer is deesterified by transesterification with an alcohol under acidic or basic conditions, a method in which a saponified ethylene-vinyl acetate copolymer is chlorosulfonated, etc. Among these, the method in which a chlorosulfonated ethylene-vinyl acetate copolymer is transesterified with an alcohol under acidic conditions is preferred because it requires a short reaction time.

[0026] Examples of methods for obtaining the chlorosulfonated ethylene-vinyl acetate copolymer include a solution method in which the ethylene-vinyl acetate copolymer is dissolved in a solvent inert to the halogenation reaction and carried out in a homogeneous system, and a suspension method in which the ethylene-vinyl acetate copolymer is suspended in a solvent and reacted. Of these, the solution method is preferred when the flexibility of the rubber is taken into consideration.

[0027] The synthesis method of chlorosulfonated ethylene-vinyl acetate copolymer by the solution method is shown below.

[0028] After dissolving the ethylene-vinyl acetate copolymer in a solvent, a radical generator and a chlorosulfonating agent are added. The reaction temperature is not particularly limited, but is 60 to 180°C. The reaction pressure is not particularly limited, but is suitably normal pressure to 1.0 MPa. Examples of solvents for dissolving the ethylene-vinyl acetate copolymer include chloroform, carbon tetrachloride, 1,1,2-trichloroethane, and chlorobenzene. Examples of radical generators include α,α'-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile). Examples of organic peroxides include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, and t-butyl perbenzoate. Azo compounds are preferred because of their high handling stability, and α,α'-azobisisobutyronitrile is particularly preferred because it allows for moderate chlorination and chlorosulfonation reactions. Examples of chlorosulfonating agents include chlorine gas and sulfurous acid gas, chlorine gas and sulfuryl chloride, sulfurous acid gas and sulfuryl chloride, sulfuryl chloride alone, and chlorine gas, sulfurous acid gas and sulfuryl chloride. When sulfuryl chloride is used as the chlorosulfonating agent, an amine compound such as pyridine, quinoline, dimethylaniline, or piperidine may be used as a co-catalyst, if necessary. After the reaction is complete, the hydrogen chloride and sulfurous acid gas dissolved in the solution are removed from the reaction system by blowing in an inert gas such as nitrogen under solvent reflux. The resulting chlorosulfonated ethylene-vinyl acetate copolymer can be separated into polymer and solvent by steam distillation, drum drying, extrusion drying, or the like, as needed.

[0029] The following describes a method for synthesizing a hydroxyl-containing chlorosulfonated polyolefin using an ester exchange reaction of a chlorosulfonated ethylene-vinyl acetate copolymer with an alcohol under acidic conditions. The chlorosulfonated ethylene-vinyl acetate copolymer is dissolved in a solvent, and then an acid and an alcohol are added. The reaction temperature is not particularly limited, but is generally 10 to 100°C. Examples of solvents for dissolving the chlorosulfonated ethylene-vinyl acetate copolymer include halogenated organic solvents such as chloroform, methylene chloride, and 1,1,2-trichloroethane, and aromatic organic solvents such as benzene, toluene, and xylene. The acid used in the reaction may be any acid that dissolves in a mixture of the solvent and alcohol, such as hydrogen chloride, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Hydrogen chloride is preferred because it is easily removed after the reaction. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, and n-butanol. Primary alcohols are preferred because of their fast reaction rate. Alcohols with four or fewer carbon atoms are also preferred because they are easily removed. Methanol is particularly preferred because of its fast reaction rate and ease of removal. After the reaction is completed, examples of methods for separating the polymer from the reaction solution include a method of distilling off the solvent under reduced pressure, a method of distilling off the solvent using a drum dryer, and a reprecipitation method in which the reaction solution is introduced into a poor solvent such as methanol to isolate the polymer.

[0030] The method for crosslinking the hydroxyl-containing chlorosulfonated polyolefin is not particularly limited, but examples include a method in which a crosslinking agent is added to a solution of the hydroxyl-containing chlorosulfonated polyolefin dissolved in an organic solvent or the like, the solution is applied to a substrate or the like, the solvent is dried, and then the crosslinking is carried out by aging. In order to broaden the range of application of substrates, the drying and aging temperatures are preferably 120°C or lower, more preferably 80°C or lower. Furthermore, for ease of operation, drying and aging are preferably carried out in a gear oven or the like.

[0031] The organic solvent for dissolving the hydroxyl group-containing chlorosulfonated polyolefin is not particularly limited, but is preferably one in which the hydroxyl group-containing chlorosulfonated polyolefin dissolves uniformly and which volatilizes under dry conditions. Examples of such organic solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, methyl acetate, ethyl acetate, normal propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methoxybutyl acetate, amyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, normal propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, methyl butyrate, normal propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl isobutyrate, normal propyl isobutyrate, isopropyl isobutyrate, butyl isobutyrate, isobutyl isobutyrate, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, dibutyl ketone, and diisobutyl ketone.

[0032] The crosslinking agent for crosslinking the hydroxyl group-containing chlorosulfonated polyolefin is not particularly limited, but examples thereof include polyisocyanates having two or more isocyanate groups per molecule, epoxy compounds having two or more epoxy groups per molecule, and sulfur. Polyisocyanates are preferred as crosslinking agents due to their excellent low-temperature crosslinking properties and the mechanical properties of the crosslinked product. Examples of polyisocyanates include, but are not limited to, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, and 1,6-hexamethylene diisocyanate. , 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, isocyanate-containing prepolymers obtained by reacting these with polyols, and mixtures of two or more of these. Furthermore, modified products of these isocyanates (modified products containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, an isocyanurate group, an amide group, an imide group, a uretonimine group, a uretdione group, or an oxazolidone group) and condensates (sometimes referred to as polynuclear compounds) such as polymethylene polyphenylene polyisocyanate (polymeric MDI) are also included.Aliphatic isocyanates are preferred because they provide crosslinked products with excellent mechanical properties and little yellowing, and examples thereof include 1,6-hexamethylene diisocyanate and modified products thereof (modified products containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, an isocyanurate group, an amide group, an imide group, a uretonimine group, a uretdione group, or an oxazolidone group). These polyisocyanates may be used alone or in combination of two or more.

[0033] When polyisocyanate is used as the crosslinking agent, a catalyst for accelerating the crosslinking reaction may be added. The catalyst for accelerating the crosslinking reaction is not particularly limited, but examples thereof include organometallic compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dioctyltin dilaurate, and organic amines such as triethylenediamine and triethylamine, and salts thereof.

[0034] When crosslinking the hydroxyl group-containing chlorosulfonated polyolefin, additives such as epoxy resins, coating improvers, leveling agents, antifoaming agents, stabilizers such as antioxidants and ultraviolet absorbers, plasticizers, surfactants, pigments (e.g., titanium oxide), fillers (e.g., talc, calcium carbonate, silica, carbon, petroleum resins, tar, asphalt), organic or inorganic fine particles, antifungal agents, and silane coupling agents may be blended as needed.

[0035] The hydroxyl group-containing chlorosulfonated polyolefin can be used as a urethane-forming composition containing the hydroxyl group-containing chlorosulfonated polyolefin and the polyisocyanate. The urethane-forming composition can be cured to form a polyurethane.

[0036] The uses of the hydroxyl group-containing chlorosulfonated polyolefin, which is one embodiment of the present invention, are not particularly limited, and examples thereof include paints and coatings, and the paints and coatings may contain the polyurethane. [Example]

[0037] EXAMPLES Next, the present invention will be specifically explained based on examples, but the present invention should not be construed as being limited to these examples.

[0038] The values ​​used in these examples were obtained in accordance with the following measurement methods.

[0039] <Chlorine content and sulfur content> The chlorine and sulfur contents of hydroxyl-containing chlorosulfonated polyolefin and chlorosulfonated ethylene-vinyl acetate copolymer were measured by the combustion flask method. To measure the chlorine content, approximately 20 mg of hydroxyl-containing chlorosulfonated polyolefin was combusted according to the oxygen flask combustion method, and 15 mL of a 1.7 wt.% hydrazinium sulfate aqueous solution was allowed to stand as an absorption solution. After 40 minutes, the absorption solution was washed out with approximately 100 mL of pure water, and then the chloride ions were quantified by potentiometric titration with a 0.5 N silver nitrate aqueous solution to measure the chlorine content.

[0040] The sulfur content of hydroxyl-containing chlorosulfonated polyolefin was measured by burning approximately 10 mg of hydroxyl-containing chlorosulfonated polyolefin using the oxygen flask combustion method and allowing it to stand with approximately 10 mL of 3 wt% hydrogen peroxide solution as an absorption solution. After 40 minutes, the absorption solution was washed out with approximately 40 mL of pure water, and then approximately 1 mL of acetic acid, approximately 100 mL of 2-propanol, and approximately 0.47 mL of Arsenazo III were added. The sulfate ions in this solution were determined by photometric titration with a 0.01 N barium acetate solution, and the sulfur content was measured.

[0041] <Acetoxy group content> The acetoxy group content of hydroxyl group-containing chlorosulfonated polyolefin and chlorosulfonated ethylene-vinyl acetate copolymer is 1 Measurement was performed by H-NMR. 1 Approximately 100 mg (W) of hydroxyl group-containing chlorosulfonated polyolefin or chlorosulfonated ethylene-vinyl acetate copolymer P ) was dissolved in approximately 1 mL of deuterated chloroform, and approximately 8.8 mg of benzene (W B ) was added and measured by NMR at 400 Hz.1 H-NMR analysis was carried out. 1 From the H-NMR chart, benzene (7.35 ppm) and C H -OAc (4.73-5.47 ppm) integral value (S B , S Ac ) was calculated, and the acetoxy group content was calculated using formula (1).

[0042] Acetoxy group content (mmol / 100g) = W B ×S Ac x10 5 / (W P ×S B ×78.11 / 6) ···(1) <Hydroxyl group content> 1 The acetoxy group content (Ac) of hydroxyl-containing chlorosulfonated polyolefins was measured by H-NMR. RM ) and the acetoxy group content (Ac SM ) and the amount of hydroxyl groups was calculated from equation (2).

[0043] Hydroxyl group content (mmol / 100g) = (Ac SM ×100 / (100-42.04×Ac SM / 1000))-(Ac SM ×100 / (100-42.04×Ac SM / 1000))×Ac RM / Ac SM ···(2) <Molecular weight measurement> The molecular weight of the hydroxyl-containing chlorosulfonated polyolefin was measured by GPC of the polymer solution obtained by dissolving 10 mg of the hydroxyl-containing chlorosulfonated polyolefin in 10 mL of THF. The weight average molecular weight (Mw) was calculated in terms of polystyrene using standard polystyrene (manufactured by Tosoh Corporation). The measurement conditions are shown below.

[0044] Model: (Product name) HLC8220GPC Solvent: THF Column temperature: 40℃ ·Measurement concentration: 10mg / 10mL ·Injection volume: 200μL Column: TSKgel G7000HXL (Tosoh Corporation) → TSKgel GMHXL (Tosoh Corporation) x 2 <Tensile test> The tensile strength (TB) and elongation at break (EB) were measured in accordance with JIS K 6251. The measurement conditions are shown below.

[0045] Test equipment: VG-1G (manufactured by Toyo Seiki Co., Ltd.) Measurement conditions: 25°C x 50% RH Head speed: 200mm / min Dumbbells: No. 4 <Synthesis of chlorosulfonated ethylene-vinyl acetate copolymer 1> In a 40 L glass-lined autoclave under a nitrogen atmosphere, 2.6 kg of ethylene-vinyl acetate copolymer (Ultrathene 520F, manufactured by Tosoh Corporation) with a melt mass flow rate (JIS K 6924-1) of 2.0 g / 10 min and a vinyl acetate content of 8 wt% was dissolved in 12 L of 1,1,2-trichloroethane (manufactured by Tosoh Corporation) at 110 °C. A solution of 1.8 g of α,α'-azobisisobutyronitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) dissolved in 1 kg of 1,1,2-trichloroethane and 5.6 kg of sulfuryl chloride (manufactured by Sumitomo Seika Chemicals Co., Ltd.) were added dropwise to this polymer solution over 140 minutes at 110 °C. The pressure inside the reactor was maintained at 0.25 MPa during the reaction. After the completion of the dropwise addition, the reaction was continued for 30 minutes, followed by nitrogen blowing for 2 hours. The reaction solution was dried in a drum dryer heated to 155° C. to remove the solvent, and chlorosulfonated ethylene-vinyl acetate copolymer 1 was obtained.

[0046] The chlorine content of the obtained chlorosulfonated ethylene-vinyl acetate copolymer 1 was 35.1% by weight, the sulfur content was 0.9% by weight, and the acetoxy group content was 56 mmol / 100 g.

[0047] <Synthesis of chlorosulfonated ethylene-vinyl acetate copolymer 2> Chlorosulfonated ethylene-vinyl acetate copolymer 2 was obtained in the same manner as in the synthesis of chlorosulfonated ethylene-vinyl acetate copolymer 1, except that the condition for the synthesis of chlorosulfonated ethylene-vinyl acetate copolymer 1 was changed from "a solution of 1.8 g of α,α'-azobisisobutyronitrile dissolved in 1 kg of 1,1,2-trichloroethane and 5.6 kg of sulfuryl chloride were added dropwise over 140 minutes" to "a solution of 1.6 g of α,α'-azobisisobutyronitrile dissolved in 0.9 kg of 1,1,2-trichloroethane and 4.4 kg of sulfuryl chloride were added dropwise over 120 minutes."

[0048] The chlorine content of the obtained chlorosulfonated ethylene-vinyl acetate copolymer 2 was 30.2% by weight, the sulfur content was 1.0% by weight, and the acetoxy group content was 60 mmol / 100 g.

[0049] Example 1 140 g of chlorosulfonated ethylene-vinyl acetate copolymer 1 was dissolved in 1260 g of 1,1,2-trichloroethane and heated to 65°C. 123 g of a 6 wt% hydrogen chloride / methanol solution was added dropwise to this polymer solution over 2 hours. After the dropwise addition was completed, nitrogen was blown in for 1 hour, the solvent was removed using an evaporator, and the residue was dried in a vacuum dryer to obtain hydroxyl group-containing chlorosulfonated polyolefin 1.

[0050] The obtained hydroxyl group-containing chlorosulfonated polyolefin 1 had a chlorine content of 35.5 wt %, a sulfur content of 0.9 wt %, an acetoxy group content of 31 mmol / 100 g, and a hydroxyl group amount of 26 mmol / 100 g.

[0051] 247 parts by weight of toluene (Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 100 parts by weight of the obtained hydroxyl-containing chlorosulfonated polyolefin 1 and dissolved. 5.9 parts by weight of polyisocyanate (Coronate HXR, NCO content 21.9% by weight, Tosoh Corporation) and 0.01 parts by weight of catalyst were added to the toluene solution of hydroxyl-containing chlorosulfonated polyolefin 1, and the mixture was mixed and degassed using a planetary centrifugal mixer (Thinky Corporation, ARE-310) to obtain a composition for property evaluation. The composition was applied to release paper to a dry film thickness of 100 μm, allowed to stand at room temperature for 90 minutes, then heated in a dryer at 60°C for 30 minutes and then at 80°C for 30 minutes to remove the solvent, and then heat-treated at 50°C for 18 hours to obtain a crosslinked product. The tensile properties of this crosslinked product were measured. The results are shown in Table 1. As can be seen from Table 1, the crosslinked product had excellent tensile properties, with a TB of 24.0 MPa and an EB of 250%.

[0052] Example 2 A hydroxyl group-containing chlorosulfonated polyolefin 2 was obtained in the same manner as in Example 1, except that the condition in Example 1, "123 g of a 6 wt % hydrogen chloride / methanol solution was added dropwise over 2 hours," was changed to "69 g of a 6 wt % hydrogen chloride / methanol solution was added dropwise over 1 hour."

[0053] The resulting hydroxyl group-containing chlorosulfonated polyolefin 2 (B-2) had a chlorine content of 35.2 wt %, a sulfur content of 0.9 wt %, an acetoxy group content of 47 mmol / 100 g, and a hydroxyl group amount of 8.6 mmol / 100 g.

[0054] A crosslinked body was obtained in the same manner as in Example 1, except that 253 parts by weight of toluene and 8.3 parts by weight of polyisocyanate were used per 100 parts by weight of the obtained hydroxyl group-containing chlorosulfonated polyolefin 2 (B-2). The tensile properties of this crosslinked body were measured. The results are shown in Table 1. As can be seen from Table 1, the crosslinked body had excellent tensile properties, with a TB of 20.8 MPa and an EB of 310%.

[0055] Example 3 A hydroxyl group-containing chlorosulfonated polyolefin 3 (B-3) was obtained in the same manner as in Example 1, except that chlorosulfonated ethylene-vinyl acetate copolymer 2 was used instead of chlorosulfonated ethylene-vinyl acetate copolymer 1 in Example 1, and the conditions of "123 g of a 6 wt % hydrogen chloride / methanol solution was added dropwise over 2 hours" were changed to "65 g of a 6 wt % hydrogen chloride / methanol solution was added dropwise over 1 hour."

[0056] The resulting hydroxyl group-containing chlorosulfonated polyolefin 3 (B-3) had a chlorine content of 30.3 wt %, a sulfur content of 1.0 wt %, an acetoxy group content of 49 mmol / 100 g, and a hydroxyl group amount of 11 mmol / 100 g.

[0057] A crosslinked body was obtained in the same manner as in Example 1, except that 259 parts by weight of toluene and 10.8 parts by weight of polyisocyanate were used per 100 parts by weight of the obtained hydroxyl group-containing chlorosulfonated polyolefin 3 (B-3). The tensile properties of this crosslinked body were measured. The results are shown in Table 1. As can be seen from Table 1, the crosslinked body had excellent tensile properties, with a TB of 9.1 MPa and an EB of 210%.

[0058] Comparative Example 1 A crosslinked product was obtained in the same manner as in Example 1, except that 257 parts by weight of toluene and 10 parts by weight of polyisocyanate were used relative to 100 parts by weight of chlorosulfonated ethylene-vinyl acetate copolymer 1 (A-1). The tensile properties of this crosslinked product were measured. The results are shown in Table 1. As can be seen from Table 1, the TB in the tensile properties was 0.5 MPa and the EB was 1900%, indicating insufficient crosslinking.

[0059] Comparative Example 2 A crosslinked product was obtained in the same manner as in Example 1, except that 250 parts by weight of toluene, 5 parts by weight of an acid acceptor for CSM (trade name: Kyowamag #150, manufactured by Kyowa Chemical Industry Co., Ltd.), and 2 parts by weight of a vulcanizing agent for CSM (trade name: Noccela TRA, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) were used per 100 parts by weight of chlorosulfonated polyethylene (trade name: TOSO-CSM CN-1500, chlorine content 30% by weight, sulfur content 1.4% by weight, manufactured by Tosoh Corporation). The tensile properties of this crosslinked product were measured. The results are shown in Table 1. As can be seen from Table 1, the TB was 0.5 MPa and the EB was 1300%, indicating insufficient crosslinking.

[0060] [Table 1] [Industrial Applicability]

[0061] The hydroxyl group-containing chlorosulfonated polyolefin of the present invention can be crosslinked at low temperatures, and therefore can be used as a crosslinked product obtained by crosslinking and molding in the same manner as conventional chlorosulfonated polyolefins, and can be used in a wide range of applications.

Claims

1. A hydroxyl group-containing chloropolymer having chlorine, chlorosulfone groups, and hydroxyl groups in a polyolefin skeleton. Sulfonated polyolefin.

2. The hydroxyl group-containing chlorosulfonate according to claim 1, wherein the chlorine content is 20 to 50% by weight. Polyolefin.

3. 3. The composition according to claim 1 or 2, wherein the content of sulfur derived from the chlorosulfonic acid group is 0.1 to 3% by weight. The hydroxyl group-containing chlorosulfonated polyolefin described above.

4. 4. The method according to claim 1, wherein the content of the hydroxyl group is 3 to 100 mmol / 100 g. The hydroxyl group-containing chlorosulfonated polyolefin described above.

5. The hydroxyl group-containing chloropolymer according to any one of claims 1 to 4, having a number average molecular weight of 10,000 to 150,000. Sulfonated polyolefin.

6. 6. The method according to claim 1, wherein the polyolefin skeleton further contains an acetoxy group. The hydroxyl group-containing chlorosulfonated polyolefin described above.

7. The water-soluble polymer according to claim 6, wherein the content of the acetoxy group is 300 mmol / 100 g or less. Acid group-containing chlorosulfonated polyolefin.

8. A urethane-forming composition comprising the hydroxyl group-containing chlorosulfonated polyolefin according to any one of claims 1 to 7 and a polyisocyanate.

9. A polyurethane which is a cured product of the urethane-forming composition according to claim 8.

10. A paint comprising the polyurethane of claim 9.

11. A coating comprising the polyurethane of claim 9.

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