CN110577623B - Epoxy-terminated polysulfide rubber modified SIS, preparation method thereof and application thereof in adhesive - Google Patents
Epoxy-terminated polysulfide rubber modified SIS, preparation method thereof and application thereof in adhesive Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
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- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
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Abstract
The invention discloses an epoxy-terminated polysulfide rubber modified SIS, a preparation method thereof and application thereof in an adhesive. The preparation process of the modified SIS comprises the following steps: obtaining styrene-isoprene segmented copolymer sol containing active terminal lithium through anionic polymerization, and coupling the styrene-isoprene segmented copolymer sol by using epoxy-terminated polysulfide rubber to obtain the epoxy-terminated polysulfide rubber modified styrene-isoprene segmented copolymer; the polymer retains the original mechanical properties of the styrene-isoprene block polymer, endows polysulfide rubber with low-temperature flexibility, weather resistance and aging resistance, simultaneously improves the polarity of the styrene-isoprene block polymer, gives affinity and adhesiveness between the modified styrene-isoprene block polymer and a polar material, is applied as an adhesive material, increases the cohesive force, and improves the adhesive strength.
Description
Technical Field
The invention relates to a modified SIS rubber material, in particular to a method for preparing modified SIS of epoxy-terminated polysulfide rubber by using the epoxy-terminated polysulfide rubber as a coupling agent of an anionic polymer SIS, and also relates to the use of the modified SIS of the epoxy-terminated polysulfide rubber as an adhesive material, belonging to the technical field of modified SIS rubber.
Background
The traditional styrene-isoprene block polymer (SIS) has linear and star structures, and the linear structure is SIS (SIS-1209) produced by the synthetic rubber division of the country petrochemical company, the holy petrochemical company, and the like; coupling agents for polymers having a star structure include silicon tetrachloride, alkoxysilanes, and the like, as coupling agents for active lithium polymers, and examples thereof include SIS-1106 and the like. The styrene-isoprene block polymer is non-polar, and is mainly used as shoe material, adhesive, etc. Coupling agents such as those used in SIS 1106 and the like are mainly dichlorodimethylsilane and the like. However, such a polymer modified with a low-molecular polar substance has a weak point of low adhesion as an adhesive. As an application of general non-polar SIS, for example, Chinese patent (CN101864259A) discloses an SIS hot melt adhesive for bonding car lamps and a preparation method thereof, wherein the SIS hot melt adhesive comprises SIS thermoplastic elastomer, plasticizer, tackifier, filler, antioxidant, wax and coupling agent, and a modifier polyphenylene oxide oligomer is added. For another example, a chinese patent (CN105086893A) discloses a medical hot melt adhesive, which comprises the following raw materials in parts by weight: 30-70 parts of graft product of SIS and PEG, 10-20 parts of naphthenic oil, 1-5 parts of antioxidant, 30-60 parts of hydrogenated petroleum resin and 5-10 parts of SAP #. The hot melt adhesive prepared from the SIS belongs to a low-end product, and the cohesive force of an adhesive cohesive layer is low, so that the hot melt adhesive is not suitable for serving as a structural adhesive. However, when a polar group is introduced into the molecular chain of the SIS, the polarity of the SIS is changed and the SIS is functionalized, so that the adhesion and the compatibility of the modified SIS and a polar material can be enhanced. Namely, the application field of the SIS after the polarization modification is expanded. Chinese patent (CN03118381.6) discloses a polarized SDS and a preparation method thereof, specifically introducing a tetrablock copolymer with the structure "SDSM", wherein S represents a polystyrene block, D may be a polyisoprene block, M represents a polar block, and the polar block is represented by the chemical general formula: CH (CH) 2 CHC(CH 3 )COO(C n H 2n+1 ) The preparation method is in the process of SDS productionAfter the third stage of polymerization, adding a polar monomer capable of performing active polymerization into the obtained SDS triblock active polymer to continue polymerization, thereby preparing the polar SDS with a section of polar monomer chain segment at the tail end. The polarized SDS is a block copolymer, the content of polar monomers can be controlled at will, and the polarized SDS can be used as an adhesive, so that the adhesive property of the polarized SDS to polar materials can be greatly improved, and compared with SIS, the peel strength can be improved by more than 50%.
The traditional polysulfide rubber with mercaptan at the tail end of a molecular chain is rubber, and the polysulfide rubber has the advantages of low-temperature flexibility, solvent resistance, stress relaxation, weather resistance, aging resistance and the like after being vulcanized, and is mainly used for manufacturing oil delivery rubber pipes, automobile oil tanks, sealing gaskets, deformation shrinkage joints of airport runways and buildings, printing rubber rollers, sealing rings, sealing adhesives and the like. Is a synthetic rubber obtained by polycondensation of a dihaloalkane and a polysulfide of an alkali metal or an alkaline earth metal. The liquid polysulfide rubber is cured and molded by condensation of thiol at the molecular chain terminal with metal oxide or ring-opening crosslinking with oligomer of epoxy group, but the liquid polysulfide rubber cannot be used as a coupling agent of anion polymerization active lithium. To date, no literature has been reported on the use of epoxidized polysulfide rubber as a technique for modifying the terminal ends of the molecular chain of anionic polymer SIS.
Disclosure of Invention
In view of the defects of the prior low molecular weight compound used for modifying the anionic SIS polymer, the first object of the invention is to provide an epoxy-terminated polysulfide rubber modified styrene-isoprene block copolymer, which retains the original mechanical properties of the styrene-isoprene block polymer, endows polysulfide rubber with low-temperature flexibility, weather resistance and aging resistance, simultaneously improves the polarity of the styrene-isoprene block polymer, endows the modified styrene-isoprene block polymer with affinity and adhesiveness with polar materials, increases the cohesive force, and improves the adhesive strength.
The second purpose of the invention is to provide a method for preparing the epoxy-terminated polysulfide rubber modified styrene-isoprene block copolymer with simple steps and low cost.
The third purpose of the invention is to provide an application of the epoxy-terminated polysulfide rubber modified styrene-isoprene block copolymer as an adhesive, wherein the modified styrene-isoprene block copolymer maintains the original mechanical properties of the styrene-isoprene block copolymer, introduces low-temperature flexibility, weather resistance and aging resistance through polysulfide rubber, improves the polarity of the styrene-isoprene block copolymer, the affinity and the adhesion between the styrene-isoprene block copolymer and polar materials, increases the cohesive force, and improves the adhesion strength.
In order to achieve the above technical object, the present invention provides an epoxy-terminated polysulfide rubber modified SIS having a structure of formula 1:
wherein the content of the first and second substances,
a is 3-28;
b is 1-4;
r is a terminator residue;
R 1 is a block copolymerization chain segment of isoprene and styrene;
R 2 is C 1 ～C 10 An alkyl chain or an alkoxy ether chain.
Preferred embodiment, R 1 Has a number average molecular weight of 3X 10 4 ～8×10 4 . More preferably 4X 10 4 ～6×10 4 。
Preferred embodiment, R 1 The block ratio (mass ratio) of the isoprene to the styrene is (20-40)/(80-60). More preferably (22-38)/(78-62).
In a preferred embodiment, R is hydrogen or alkyl (alkyl is lower alkyl, generally lower than C) 5 )。
Preferably, the number average molecular weight of the epoxy-terminated polysulfide rubber modified SIS is 8X 10 4 ～18×10 4 And the melt index is 0.01-8.0 g/10 min.
The invention also provides a preparation method of the modified SIS of the epoxy-terminated polysulfide rubber, the method obtains SIS sol containing active terminal lithium through anionic polymerization, and the SIS sol is obtained by coupling the epoxy-terminated polysulfide rubber.
Preferably, the end-epoxy-group polysulfide rubber has a structure of formula 2:
wherein the content of the first and second substances,
a is 3 to 28;
b is 1-4;
R 2 is C 1 ～C 10 An alkyl chain or an alkoxy ether chain.
Preferably, the molar ratio of active lithium to the epoxy group of the epoxy-terminated polysulfide rubber in the SIS sol is 1: 1-1.5.
In the preferable scheme, in the coupling process, the reaction temperature is 50-70 ℃ and the time is 30-35 min.
In the preparation process of the modified SIS of the end epoxy group-terminated polysulfide rubber, water or alcohols are used for terminating the reaction after the coupling reaction is finished.
The invention also provides an application of the modified SIS of the epoxy-terminated polysulfide rubber, which is used as an adhesive material.
Preferred embodiments, the adhesive formulations of the present invention are conventional in the art. The adhesive formula comprises the following components in parts by mass: 100 parts of end-epoxy-group polysulfide rubber modified SIS, 25-35 parts of naphthenic oil, 10761-2 parts of antioxidant and 100-150 parts of rosin resin. Most preferred formulations are: for example, 100 parts of epoxy-terminated polysulfide rubber modified SIS, 30 parts of naphthenic oil, 10761.5 parts of antioxidant and 120 parts of rosin resin.
According to the preparation method of the adhesive, the components of the adhesive are stirred for 2.5 hours at 180-190 ℃ to prepare the hot melt adhesive.
According to the preparation method of the epoxy-terminated polysulfide rubber modified SIS, the SIS is synthesized by the conventional method. Firstly, styrene is initiated to polymerize by butyl lithium, then isoprene is added for copolymerization to prepare a diblock isoprene-styrene block copolymer containing active lithium at the tail end, and finally the active polymer is subjected to coupling reaction by liquid polysulfide rubber at the end of an epoxy group, thus obtaining the polymer. N-butyllithium initiator may be used to initiate the polymerization during the polymerization. An activator THF is adopted to improve the polymerization rate of the isoprene monomer, and the concentration of the THF in a solvent is 20-100 mg/kg; the temperature of butyl lithium initiated styrene is 40-60 ℃, and the time is 20-25 min; the polymerization temperature of the second-stage isoprene is 40-90 ℃, and the time is 20-25 min.
The preparation method of the end epoxy group-terminated polysulfide rubber comprises the steps of reacting the polysulfide rubber with an alkyl lithium reagent in advance, and converting thiol groups in the polysulfide rubber into sulfur-lithium bonds to obtain a sulfur-lithium polymer; and then carrying out end-capping reaction on the lithium sulfide polymer and a halogenated epoxy organic raw material to obtain the lithium sulfide/epoxy resin composite material.
The polysulfide rubber of the invention has a structure of formula 3:
wherein a is an integer of 3 to 28, and b is an integer of 1 to 4.
The preferable number average molecular weight of the polysulfide rubber is 1000 to 5000. A functionality of 2.1 to 2.7. The mass content of HS-group (mercapto) is 1.2-7.7%, and the viscosity is 7.5-200 Pa.s.
The polysulfide rubber of the invention can be selected from series products such as LP or JLY type products and the like which are sold in the market.
The halogenated epoxy organic raw material has a structure shown in a formula 4:
wherein R is 2 Is C 1 ～C 10 An alkyl chain of, or C 1 ～C 10 An alkoxy ether chain, and X is halogen.
The preparation method of the epoxy-terminated liquid polysulfide rubber comprises two steps, wherein the first step is to mix the liquid polysulfide rubber (formula 3) with a solvent, and to add quantitative lithium alkyl (R) under the technological conditions of no oxygen, no water vapor and the like while stirring 3 Li，R 3 Alkyl), the thiol group (-SH) in the polysulfide rubber molecule is converted into a sulfur lithium bond (-SLi), and a sulfur lithium polymer (formula A) is obtained; and in the second step (also called end-capping reaction), adding a certain amount of epoxy organic chlorine raw material (formula 4) into the reaction solution to condense with the lithium sulfur group of formula A, and introducing epoxy groups into the ends of the polysulfide rubber molecules to obtain the end-epoxy-terminated polysulfide rubber (formula B). The reaction circuit is as follows:
the process conditions of the first step reaction are as follows: the reaction environment is preferably anhydrous and anaerobic and is carried out under the protection of nitrogen or argon, and the reaction solvent is aromatic solvent; preferably at least one of benzene, toluene and xylene. The mass content of the polysulfide rubber in the solvent is selected to be 20-50%. The alkyl lithium has the formula R 3 Li, preferably n-butyllithium and/or sec-butyllithium; most preferably, the concentration of the alkyllithium in the solvent is 0.5 to 1.0 mol/L. The dosage of the alkyl lithium is 1.05-1.1 times of the theoretical molar weight of the complete reaction of the mercaptan in the polysulfide rubber. The reaction temperature is 10-80 ℃. The reaction time is 20-40 min. After the alkyl lithium and the polysulfide rubber react, adding a terminator for terminating the excessive alkyl lithium into the reaction system, and then adding the epoxy organic chlorine raw material to carry out end-capping reaction. The terminating agent is alcohol or ketone, so that the excessive butyl lithium is terminated, and the next step of ring-opening reaction between the excessive butyl lithium and the epichlorohydrin is avoided. The amount of the terminator is 5-10% of the total mass of the butyl lithium. The reaction is stopped at 10-80 ℃ for 20 min.
The conditions of the second step reaction: the dosage of the halogenated epoxy organic raw material is 1.05 to 1.1 times of the theoretical dosage of completely blocking the polysulfide rubber. The temperature of the end-capping reaction is 50-80 ℃. The end capping reaction time is 60-120 min. And after the end-capping reaction is finished, adding water into the reaction system, separating out a water phase, and removing the solvent from the residual material to obtain the epoxy-terminated polysulfide rubber.
The invention discloses an end epoxy group polysulfide rubber, which has a structure shown in formula 2:
wherein the content of the first and second substances,
a is 3-28;
b is 1 to 4;
R 2 is C 1 ～C 10 An alkyl chain or an alkoxy ether chain (e.g., an oligoethylene glycol such as an oligoethylene glycol having an oxygen atom number of 2, 3 or 4).
The molecular structure of the epoxy terminated polysulfide rubber only contains ethylene ether, so that the rubber has better flexibility and elasticity, and overlong linear alkyl group shows plasticity and the rebound resilience is reduced. The number average molecular weight of the end-epoxy-group polysulfide rubber is 1000-5000; the viscosity is 7.5 to 200Pa.s, the epoxy value is 0.034 to 0.189mol/100g, and the mass content of the mercapto group is 1.2 to 7.7%.
The epoxy terminated polysulfide rubber is used as a coupling agent of terminal active lithium (S-I-Li) of an anionically polymerized styrene-isoprene block copolymer, and the coupled polysulfide rubber modified isoprene-styrene block polymer (also called as middle-end coupled SIS for short) is mainly used as a high-performance adhesive.
The epoxy-terminated polysulfide rubber is prepared into a solution with the mass percent concentration of 20-70% by an organic solvent for use. The preferable mass percentage is 40-60%; the solvent used is preferably at least one of benzene, toluene, xylene or THF, with toluene being preferred.
The epoxy-terminated polysulfide rubber modified isoprene-styrene block copolymer (middle-end coupled SIS) disclosed by the invention keeps the ethylene ether and sulfur-thioether bond of the original polysulfide rubber in the middle of the molecular chain, still can show the flexibility and elasticity of the original polysulfide rubber, and is introduced as a polar polymer chain at the middle end of the SIS.
The invention uses epoxy-terminated polysulfide rubber as coupling agent of active lithium (S-I-Li) at the end of anionic polymerization styrene-isoprene diblock copolymer, and couples to obtain polysulfide rubber modified styrene-isoprene block polymer (called (SI) n-polysulfide rubber for short), wherein the SI n-polysulfide rubber still shows the behavior of elastomer, and is mainly used as adhesive material with good adhesion.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the epoxy-terminated polysulfide rubber modified styrene-isoprene block copolymer provided by the invention introduces a polysulfide rubber molecular long chain with strong polarity into the middle section of an SIS polymer molecule, and endows the polysulfide rubber with low-temperature flexibility, solvent resistance, weather resistance, aging resistance and the like on the premise of ensuring that the original mechanical properties of the styrene-isoprene rubber are not influenced.
2) The epoxy-terminated polysulfide rubber modified styrene-isoprene block copolymer is used as an adhesive, the middle section of the modified styrene-isoprene block copolymer is a polysulfide rubber polar chain, the polysulfide rubber polar chain is a strong polar long chain, and sulfur-sulfur bonds and ether bonds with more equivalents are provided, so that the affinity and the adhesion of the modified styrene-isoprene polymer and a polar material are provided, the cohesive force is increased, and the adhesion strength is improved.
3) The polysulfide rubber modified solution polystyrene-isoprene rubber has simple polymerization and coupling processes, can be synthesized by utilizing the existing mature process, and is easy to control the reaction and industrialize.
Detailed Description
The present invention is illustrated by the following examples, which are not intended to limit the scope or practice of the invention.
And (3) measuring the physical properties of the vulcanized rubber by adopting an INSTRON tensile machine.
The epoxy value of epoxy group in the epoxy-terminated polysulfide rubber is determined by direct titration of brominated quaternary ammonium salt.
The molecular mass and molecular weight distribution index of the polymer were determined by gel permeation chromatography GPC.
The peel strength of the modified adhesive was measured using a BLD-200S type electron peel tester.
The end epoxy group-terminated polysulfide rubber is prepared by the following method:
preparation of end epoxy group-terminated polysulfide rubber (1)
The first step is that 100g of JLY-121 type polysulfide rubber (average molecular weight is 1000, viscosity is 8 pas, and mercapto mass content is 6.50%) and 400g of toluene are respectively put into a 1L clean three-neck flask, saturated water in materials is removed by an azeotropic dehydration method, then the temperature is reduced to below 80 ℃, under the protection of nitrogen and stirring, under the temperature of 10-80 ℃ of reaction liquid, 206mL of 1.0mol/L n-butyl lithium is continuously dropped into the reaction liquid in the flask within 20min, then the reaction liquid is reacted for 40min, and 0.6mL of ethanol is sucked by an injector and injected into the reaction flask for terminating the reaction for 20 min.
And the second step is to add 18.5g of epoxy chloropropane into the reaction liquid in the first step, stir the mixture for reaction for 60min at 50-80 ℃, add 20mL of deionized water into the reaction liquid, stir the mixture for 15min, stand the mixture to remove a water phase, and finally remove the solvent and other low-boiling organic impurities by a reduced pressure distillation method at 100-110 ℃ and-0.05 MPa to obtain the amber viscous liquid. The viscosity of the end-ring oxidized polysulfide rubber was measured by analysis to be 8.2 pas and the epoxy value was 0.189mol/100 g.
Preparation of end epoxy group-terminated polysulfide rubber (2)
The relevant process conditions in preparation example (1) were not changed.
Only in the first step, 100g of JLY-1225 type (average molecular weight 2500, viscosity 17 pas, mercapto group mass content 2.62%) and 100g of toluene were selected as polysulfide rubber, 87mL of n-butyllithium was used, the reaction time was 30min, and 0.5mL of ethanol was added as a terminator.
And 8.08g of epoxy chloropropane is added in the second step of reaction, the reaction time is 120min, 30mL of deionized water is used for stirring for 15min after the reaction is finished, the mixture is statically separated to remove a water phase, and the solvent and other organic impurities with low boiling point are removed by reduced pressure distillation. The viscosity of the amber viscous liquid was found by analysis to be 18.5 pas and the epoxy value to be 0.076mol/100 g.
Preparation of end epoxy group-terminated polysulfide rubber (3)
The relevant process conditions in preparation example (1) were unchanged.
Only in the first step, 100g of JLY-124 type (average molecular weight 4000, viscosity 70pa. S, mercapto mass content 1.64%) and 300g of toluene were selected as polysulfide rubber, 54mL of n-butyllithium was used, the reaction time was 25min, and 0.4mL of terminating agent ethanol was added.
4.8g of epichlorohydrin is added in the second step of reaction, the reaction time is 80min, 40mL of deionized water is used for stirring for 15min after the reaction is finished, the mixture is statically separated to remove a water phase, and a reduced pressure distillation method is used for removing a solvent and other organic impurities with low boiling point. The viscosity of the amber viscous liquid was determined by analysis to be 72.1 pas and the epoxy value to be 0.048mol/100 g.
Preparation of end epoxy group-terminated polysulfide rubber (4)
The relevant process conditions in preparation example (1) were unchanged.
Only in the first step, 100g of JLY-155 type (average molecular weight 5000, viscosity 96 Pa.s, mercapto mass content 1.24%) and 400g of toluene were selected as polysulfide rubber, 79mL of 0.5mol/L n-butyllithium was used, the reaction time was 20min, and 0.3mL of ethanol was added as a terminator.
And 3.8g of epoxy chloropropane is added in the second step of reaction, the reaction time is 60min, 40mL of deionized water is used for stirring for 15min after the reaction is finished, the mixture is statically separated to remove a water phase, and a reduced pressure distillation method is used for removing a solvent and other organic impurities with low boiling point. The viscosity of the amber viscous liquid was determined by analysis to be 98.6 pas and the epoxy value to be 0.036mol/100 g.
Example 1
Adding 3500mL of cyclohexane solution of 10% n-hexane in parts by mass into a 5L polymerization kettle under the protection of nitrogen, then adding 0.2mL of tetrahydrofuran, heating the solvent in the polymerization kettle to 50-60 ℃ with hot water, then adding 100g of styrene into the polymerization kettle, stirring, then injecting 12mL of 1.0mol/L n-butyl lithium into the polymerization kettle with an injector, and reacting for 20-25 min; adding 343mL of isoprene, and reacting for 25min at 50-90 ℃; then, 45g of the epoxy terminated polysulfide rubber solution prepared in preparation example (3) and having a toluene solution concentration of 50% by mass was added thereto, and the mixture was further heated at 55 deg.C ～ After the coupling reaction was carried out at 70 ℃ for 30 min. The polymer was discharged and 1.25g of antioxidant were added1076 adding into the glue solution, stirring, adding into boiling water, stirring for 40min, filtering to remove water, and oven drying at 80 deg.C for 2 hr. The intermediate modified SIS of the epoxy terminated polysulfide rubber with wider molecular weight distribution is obtained.
The coupled SIS was determined to be 9.21 х 10 Mn 4 ，M W ＝14.74х10 4 (ii) a Melt index 6.4g/10 min; after the sizing material is pressed into sheets, the 300% stress at definite elongation is 2.35MPa, the elongation at break is 920%, and the permanent deformation is 16%.
Example 2
The relevant process conditions in example 1 were changed to 10mL of n-butyllithium and 588mL of isoprene, and 50g of the epoxy terminated polythiorubber solution having a toluene solution mass concentration of 50% prepared in preparation example (4) was used.
The SIS after coupling was measured, Mn 12.34 х 10 4 ，M W ＝20.14х10 4 (ii) a Melt index 1.64g/10 min; after the sizing material is tabletted, the 300% stress at definite elongation is 2.15MPa, the elongation at break is 1032%, and the permanent deformation is 16%.
Example 3
100 parts of each of the SIS prepared in the examples 1-2 and the SIS-1209 of the comparative sample are respectively added with 30 parts of naphthenic oil, 10761.5 parts of antioxidant and 120 parts of rosin resin, and stirred in a 500mL beaker at 180-190 ℃ for 2.5h to prepare the hot melt adhesive. As a result, the respective adhesive strengths were measured as shown in Table 1.
TABLE 1 Peel Strength of modified SIS formulated hot melt adhesives prepared in examples 1-2
Example 4
The SIS modified by coupling the middle-end polysulfide rubber prepared in examples 1-2 and the SIS-1209 comparative sample were respectively tabletted, and then aged in a hot air aging oven at 80 ℃ for 72h, and the physical properties of each film before and after aging were measured as shown in Table 2.
TABLE 2 ageing resistance test
From the data analysis in table 2, it was found that the end epoxy modified SIS had significantly improved aging resistance compared to the general purpose SIS.
Claims (11)
1. An epoxy-terminated polysulfide rubber modified SIS, which is characterized in that: has the structure of formula 1:
formula 1
Wherein the content of the first and second substances,
a is 3-28;
b is 1-4;
r is a terminator residue;
R 1 is a block copolymerization chain segment of isoprene and styrene;
R 2 is C 1 ~C 10 An alkylene chain or an alkoxy ether chain of (2).
2. The epoxy-terminated polysulfide rubber modified SIS according to claim 1, wherein: r is 1 Has a number average molecular weight of 3X 10 4 ~8×10 4 。
3. The epoxy-terminated polysulfide rubber modified SIS according to claim 2, wherein: r 1 Wherein the block ratio of isoprene to styrene is = (20-40)/(80-60).
4. The epoxy-terminated polysulfide rubber modified SIS according to claim 1, wherein: r is hydrogen or alkyl.
5. The epoxy-terminated polysulfide rubber modified SIS according to claim 1, wherein: number average of terminal epoxy group polysulfide rubber modified SISMolecular weight of 8X 10 4 ~18×10 4 And the melt index is 0.01-8.0 g/10 min.
6. The method for preparing an epoxy-terminated polysulfide rubber modified SIS as claimed in any of claims 1 to 5, characterized in that: and (3) carrying out anionic polymerization to obtain SI sol containing active end group lithium, wherein the SI sol is obtained by coupling epoxy-terminated polysulfide rubber.
7. The method for preparing an epoxy-terminated polysulfide rubber modified SIS as claimed in claim 6, wherein: the end epoxy group polysulfide rubber has a structure of formula 2:
formula 2
Wherein, the first and the second end of the pipe are connected with each other,
a is 3 to 28;
b is 1-4;
R 2 is C 1 ~C 10 An alkylene chain or an alkoxy ether chain of (a).
8. The method for preparing an epoxy-terminated polysulfide rubber modified SIS as claimed in claim 6, wherein: the mol ratio of the active end group lithium to the epoxy group of the end epoxy group polysulfide rubber in the SI sol is 1: 1-1.5.
9. The method for preparing an epoxy-terminated polysulfide rubber modified SIS as claimed in any one of claims 6 to 8, wherein: in the coupling process, the reaction temperature is 50-70 ℃ and the time is 30-35 min.
10. Use of the epoxy-terminated polysulfide rubber modified SIS of any of claims 1 to 5, characterized in that: the adhesive is applied as an adhesive material.
11. Use of an epoxy-terminated polysulfide rubber modified SIS according to claim 10, characterized in that: the adhesive formula comprises the following components in parts by mass: 100 parts of end-epoxy-group polysulfide rubber modified SIS, 25-35 parts of naphthenic oil, 1-2 parts of antioxidant and 100-150 parts of rosin resin.
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| JP2001131343A (en) * | 1999-11-08 | 2001-05-15 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
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| JP2001131343A (en) * | 1999-11-08 | 2001-05-15 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
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