CN110240761B

CN110240761B - Rubber composition and application thereof, and vulcanized capsule and preparation method thereof

Info

Publication number: CN110240761B
Application number: CN201810191435.7A
Authority: CN
Inventors: 龚惠勤; 邱迎昕; 王丽丽; 张雷; 包巧云
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2018-03-08
Filing date: 2018-03-08
Publication date: 2022-07-12
Anticipated expiration: 2038-03-08
Also published as: CN110240761A

Abstract

The invention discloses a rubber composition and application thereof, and a vulcanized capsule and a preparation method thereof, wherein the rubber composition contains butyl rubber, a reinforcing agent and a vulcanizing agent, the butyl rubber contains a structural unit derived from isobutene, a structural unit derived from conjugated diene and an optional structural unit derived from aryl olefin, at least part of the conjugated diene is isoprene, the aryl olefin is selected from a compound shown in a formula I, in the butyl rubber, part of the structural unit derived from the conjugated diene is used as a grafting site so that part of molecular chains of the butyl rubber are grafted chains, and the rest of the molecular chains of the butyl rubber are linear chains; the peak molecular weight of the butyl rubber is 90-260 ten thousand, and the content of the butyl rubber with Log (MW) being more than or equal to 6 is 30-80 wt%. The curing bladders formed from the rubber compositions of the present invention exhibit improved service life.

Description

Rubber composition and application thereof, and vulcanized capsule and preparation method thereof

Technical Field

The invention relates to a rubber composition and application thereof, and also relates to a vulcanization capsule and a preparation method thereof.

Background

With the continuous development of the automobile industry in the world and the rapid growth of the global expressway, the types of automobiles are more and more, the running speed is higher and higher, the quality requirement on tires is higher and higher, and therefore the quality requirement on tire molds is higher and higher. The tire curing bladder is a necessary tool for a curing process in modern tire production, and is used for isolating a curing medium from the inner surface of a tire blank and simultaneously transferring heat and pressure on the inner surface of the tire blank during tire curing. Tire curing bladders are subjected to harsh operating conditions including high temperatures, substantial flexing, co-vulcanization and migration of the curing agents from the uncured green tire, and the service life of the curing bladder has a significant impact on the production efficiency of the tire plant.

Butyl rubber is the main raw material for producing the curing bladder, and although some butyl rubbers for producing the curing bladder have been developed, there is still a need to develop a novel butyl rubber to obtain a curing bladder having more excellent properties, particularly having a longer service life.

Disclosure of Invention

The invention aims to provide a curing bladder with a prolonged service life.

According to a first aspect of the present invention, there is provided a rubber composition comprising a butyl rubber, a reinforcing agent and a vulcanizing agent, wherein the butyl rubber comprises structural units derived from isobutylene, structural units derived from a conjugated diene, at least a part of which is isoprene, and optionally structural units derived from an aryl olefin selected from the group consisting of compounds represented by formula I,

in the formula I, R₁Is C₆-C₂₀Aryl of (a);

in the butyl rubber, a part of structural units derived from conjugated diene are used as grafting sites, so that a part of molecular chains of the butyl rubber are graft chains, and the rest of molecular chains of the butyl rubber are linear chains;

the peak molecular weight of the butyl rubber is 90-260 ten thousand, and the content of the butyl rubber with Log (MW) being more than or equal to 6 is 30-80 wt%.

According to a second aspect of the invention, there is provided the use of a rubber composition according to the first aspect of the invention for the preparation of a curing bladder.

According to a third aspect of the present invention, there is provided a curing bladder formed from the rubber composition of the first aspect of the present invention.

According to a fourth aspect of the present invention, there is provided a process for producing a curing bladder, which comprises mixing the components of the rubber composition of the first aspect of the present invention and then molding the mixture.

According to a fifth aspect of the invention there is provided a curing bladder prepared by the method of the fourth aspect of the invention.

The curing bladder prepared from the rubber composition according to the invention shows a significantly improved service life, up to 600 times or more and a limit life of 650 times or more.

Drawings

FIG. 1 is a graph showing the die swell ratio at 100 ℃ as a function of shear rate for rubber mixtures prepared from butyl rubbers prepared in preparation examples 1 and 2 and preparation comparative example 1.

FIG. 2 is a Gel Permeation Chromatography (GPC) graph of the butyl rubber prepared in preparation example 4.

FIG. 3 is a GPC chart of butyl rubber prepared in preparation example 6.

FIG. 4 is a GPC chart of butyl rubber prepared in preparation example 8.

FIG. 5 is a graph of the die swell ratio at 100 ℃ as a function of shear rate for the butyl rubbers prepared in preparative examples 4 and 8 and for the rubber compounds prepared in preparative comparative examples 3 and 4.

FIG. 6 is a photograph of the inside surface of the curing bladder prepared in example 1 after 589 uses.

FIG. 7 is a photograph of the inner surface of the curing bladder prepared in comparative example 2 after 450 uses.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to a first aspect of the present invention, there is provided a rubber composition comprising a butyl rubber, a reinforcing agent and a vulcanizing agent.

According to the rubber composition of the present invention, the butyl rubber contains structural units derived from isobutylene, structural units derived from a conjugated diene, at least a part of which is isoprene, and optionally structural units derived from an aryl olefin.

In the present invention, "a structural unit derived from isobutylene" means that the structural unit is formed of isobutylene, and the atomic species and the number of each atom are the same as compared with isobutylene except that the electronic structure is changed; "structural unit derived from a conjugated diene" means that the structural unit is formed from a conjugated diene, and the atomic species and the number of each atom are the same as compared with the conjugated diene except that the electronic structure is changed; "structural unit derived from an arylalkene" means that the structural unit is formed from an arylalkene, and the atomic species and the number of atoms are the same as compared with the arylalkene except that the electronic structure is changed.

The conjugated diene refers to a compound containing conjugated double bonds in a molecular structure. Preferably, the conjugated diene is selected from the group consisting of compounds of formula II,

in the formula II, R₂、R₃And R₄Same or different, each selected from hydrogen and C₁-C₅Linear or branched alkyl.

Specific examples of the conjugated diene may include, but are not limited to, butadiene and/or isoprene.

The aryl alkene refers to a substance formed by substituting at least one hydrogen atom in alkene with an aryl group. Specifically, the aryl alkene may be a compound represented by formula I:

in the formula I, R₁Is C₆-C₂₀The aryl group of (2) may be specifically selected from phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-dodecylphenyl, 2, 4-di-n-butylphenyl, n-propylphenyl and 2, 4-diethylphenyl groups.

Specific examples of the aryl olefin may include, but are not limited to, one or more of styrene, 2-methylstyrene, 4-tert-butylstyrene, 4-ethylstyrene, 3, 5-diethylstyrene, 3, 5-di-n-butylstyrene, 4-n-propylstyrene, and 4-dodecylstyrene.

Preferably, the arylalkene is styrene.

According to the rubber composition of the present invention, the butyl rubber contains structural units derived from a conjugated diene, and at least part of the conjugated diene is isoprene.

The rubber composition according to the invention, in the butyl rubber, the content of structural units derived from conjugated diene may be from 0.5 to 2.5% by mole, for example: 0.5 mol%, 0.6 mol%, 0.7 mol%, 0.8 mol%, 0.9 mol%, 1 mol%, 1.1 mol%, 1.2 mol%, 1.3 mol%, 1.4 mol%, 1.5 mol%, 1.6 mol%, 1.7 mol%, 1.8 mol%, 1.9 mol%, 2 mol%, 2.1 mol%, 2.2 mol%, 2.3 mol%, 2.4 mol%, or 2.5 mol%. Preferably, the butyl rubber has a content of structural units derived from conjugated diene of 0.8 to 2 mol%. More preferably, the butyl rubber has a content of structural units derived from conjugated diene of from 1 to 1.8 mole percent, such as from 1.2 to 1.6 mole percent.

In the rubber composition according to the present invention, in the butyl rubber, the structural unit derived from the conjugated diene may be a structural unit derived from isoprene or a combination of a structural unit derived from isoprene and a structural unit derived from other conjugated diene (such as butadiene) than isoprene. The content of the structural unit derived from isoprene in the butyl rubber may be 0.5 to 2.5 mol%, for example: 0.5 mol%, 0.6 mol%, 0.7 mol%, 0.8 mol%, 0.9 mol%, 1 mol%, 1.1 mol%, 1.2 mol%, 1.3 mol%, 1.4 mol%, 1.5 mol%, 1.6 mol%, 1.7 mol%, 1.8 mol%, 1.9 mol%, 2 mol%, 2.1 mol%, 2.2 mol%, 2.3 mol%, 2.4 mol%, or 2.5 mol%. Preferably, the butyl rubber has a content of structural units derived from isoprene of 0.8 to 2 mol%. More preferably, the butyl rubber has a content of structural units derived from isoprene in the range of 1 to 1.8 mol%, such as 1.1 to 1.4 mol%. In the present invention, the content of the structural unit derived from conjugated diene and the content of the structural unit derived from isoprene in the butyl rubber are measured by nuclear magnetic resonance hydrogen spectroscopy.

According to the rubber composition of the present invention, the butyl rubber may or may not contain a structural unit derived from an aryl olefin. In a preferred embodiment, the butyl rubber contains structural units derived from an aryl olefin. In this preferred embodiment, the structural units derived from the aryl olefin may be present in an amount of from 0.01 to 3 mole%, based on the total amount of butyl rubber, for example: 0.01 mol%, 0.02 mol%, 0.03 mol%, 0.04 mol%, 0.05 mol%, 0.06 mol%, 0.07 mol%, 0.08 mol%, 0.09 mol%, 0.1 mol%, 0.2 mol%, 0.3 mol%, 0.4 mol%, 0.5 mol%, 0.6 mol%, 0.7 mol%, 0.8 mol%, 0.9 mol%, 1 mol%, 1.1 mol%, 1.2 mol%, 1.3 mol%, 1.4 mol%, 1.5 mol%, 1.6 mol%, 1.7 mol%, 1.8 mol%, 1.9 mol%, 2 mol%, 2.1 mol%, 2.2 mol%, 2.3 mol%, 2.4 mol%, 2.5 mol%, 2.6 mol%, 2.7 mol%, 2.8 mol%, 2.9 mol%, or 3 mol%. Preferably, the structural units derived from the aryl olefin are present in an amount of 0.05 to 2.8 mole percent, based on the total amount of butyl rubber. In a more preferred embodiment, the structural units derived from the aryl olefin are present in an amount of from 0.01 to 1 mole%, preferably from 0.05 to 0.6 mole%, more preferably from 0.1 to 0.5 mole%, and even more preferably from 0.3 to 0.5 mole%, based on the total amount of butyl rubber. In the present invention, the content of structural units derived from an aryl olefin in the butyl rubber is determined by nuclear magnetic resonance hydrogen spectroscopy.

According to the rubber composition of the present invention, in the butyl rubber, a part of the structural units derived from the conjugated diene are used as graft sites so that a part of the molecular chain of the butyl rubber is a graft chain. The graft chain comprises a main chain and a branched chain bonded to a graft site on the main chain.

The backbone of the graft chain contains structural units derived from a conjugated diene and optionally structural units derived from an aryl olefin. The grafting sites in the grafted chain used to bond the backbone to the branches are typically carbon-carbon double bonds in structural units derived from conjugated dienes, such as those formed by 1, 2-polymerization and/or 3, 4-polymerization of conjugated dienes. In the backbone of the graft chain, the conjugated diene may be a conjugated diene as described above. Preferably, in the backbone of the grafted chain, the conjugated diene is preferably butadiene and/or isoprene.

In a preferred embodiment, the backbone of the grafted chain contains structural units derived from a conjugated diene as well as structural units derived from an aryl olefin. In a more preferred embodiment, the backbone of the graft chain contains structural units derived from a conjugated diene and structural units derived from styrene.

When the main chain of the graft chain contains a structural unit derived from a conjugated diene and a structural unit derived from an aryl olefin, the structural unit derived from a conjugated diene and the structural unit derived from an aryl olefin may be randomly distributed or may be present in the form of a block, and are not particularly limited.

In a preferred embodiment, the backbone of the graft chain is derived from a styrene-butadiene copolymer and/or a pentylene-benzene copolymer. The styrene-butadiene copolymer and the pentylene copolymer may be each a random copolymer, a block copolymer, or a mixture of a random copolymer and a block copolymer, and are not particularly limited.

The branches of the grafted chain generally contain structural units derived from isobutylene as well as structural units derived from isoprene.

In the rubber composition according to the present invention, the remaining molecular chains in the butyl rubber are generally linear chains. The linear chain contains structural units derived from isobutylene and structural units derived from isoprene.

The compositions according to the invention employ butyl rubbers having a higher content of high molecular weight components than commercial butyl rubbers. Generally, the butyl rubber has a polymer content of Log (MW) ≧ 6 of 30 to 80% by weight, such as: 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, or 80 wt%. Preferably, the butyl rubber has a polymer content of Log (MW) 6 or more of from 33 to 75% by weight. More preferably, the butyl rubber has a polymer content of Log (MW) ≧ 6 of 35-70% by weight, such as 35-55% by weight.

The butyl rubber in the rubber composition according to the invention has a significantly increased molecular weight compared to commercial butyl rubber. Typically, the butyl rubber has a peak molecular weight of from 90 to 260 tens of thousands, for example: 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, or 260 tens of thousands. Preferably, the butyl rubber has a peak molecular weight of 95 to 230 ten thousand. More preferably, the butyl rubber has a peak molecular weight of 100 to 210 ten thousand. Further preferably, the butyl rubber has a peak molecular weight of 110 to 190 ten thousand.

The Z-average molecular weight (M) of the butyl rubber in the rubber composition according to the invention_z) From 300 to 700 thousand, such as 300, 350, 400, 450, 500, 550, 600, 650, or 700 ten thousand. Preferably, the butyl rubber has a Z-average molecular weight of 350 to 650 ten thousand. More preferably, the butyl rubber has a Z-average molecular weight of 390 to 600 ten thousand. Further preferably, the Z-average molecular weight of the butyl rubber is 450 to 580 ten thousand.

According to the rubber composition of the invention, M of the butyl rubber_z/M_w(M_wWeight average molecular weight) of 1.8 to 5, for example: 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6. 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5. Preferably, M of the butyl rubber_z/M_wIs 2-4.5. More preferably, M of the butyl rubber_z/M_wIs 2.2-4. Further preferably, M of the butyl rubber_z/M_wIs 2.2-3.5. Even more preferably, M of the butyl rubber_z/M_wIs 2.4-3.2. M of the butyl rubber_w/M_nFrom 3 to 8, for example: 3. 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, or 8. Preferably, M of the butyl rubber_w/M_nIs 3.2-7.5. More preferably, M of the butyl rubber_w/M_nIs 3.3-7. Further preferably, M of the butyl rubber_w/M_nIs 3.4-6.

According to the rubber composition, the molecular weight of the butyl rubber is in a bimodal distribution, and a shoulder peak exists on the high molecular weight side of a rinsing peak in a gel permeation chromatography spectrogram, and is called as a high molecular weight shoulder peak in the invention. According to the rubber composition of the invention, the gel permeation chromatography spectrum of the butyl rubber has a log (mw) value of the high molecular weight shoulder between 6 and 7.5, for example: the log (mw) of the high molecular weight shoulder is between 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, or 7.5. According to the rubber composition of the present invention, the high molecular weight component of the butyl rubber is mainly derived from the grafted chains as described hereinbefore.

In the invention, the molecular weight and the distribution of the butyl rubber are measured by a gel permeation chromatography analysis method combining multiple detections and combinations, and the specific method comprises the following steps: the measurement was carried out by using a liquid gel permeation chromatograph model TDA302 manufactured by Viscotek, USA, which is equipped with a differential detector, a light scattering detector and a viscosity detector, and a column of TSKgel GMH manufactured by TOSOH_HR-L and TSKgel GMH_HR-H twoThe columns were used in combination. The mobile phase is tetrahydrofuran, and the flow rate is 1.0 mL/min; the concentration of the sample solution is 0.8 mg/mL; the test temperature was 30 ℃. The Log (MW) value of the high molecular weight shoulder and the polymer content of Log (MW) > 6 are determined from the differential distribution curve in a graph with log (MW) as abscissa and dWf/dLog (MW) as ordinate, obtained by a differential detector, MW being the molecular mass in Dalton (Da). In the present invention, the peak molecular weight (M)_p) It is a molecular weight value corresponding to the maximum concentration of a polymer in a spectrum of the concentration of the polymer versus the elution time measured by gel permeation chromatography.

According to the rubber composition of the present invention, the mooney viscosity ML (1+8)125 ℃ of the butyl rubber (i.e., raw rubber of butyl rubber) is 30 to 70, for example: 30. 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70. Preferably, the butyl rubber (i.e., the raw rubber of the butyl rubber) has a Mooney viscosity ML (1+8) at 125 ℃ of from 40 to 60.

In the present invention, the Mooney viscosity of the butyl rubber was measured at 125 ℃ C (1+8) by using a Mooney viscometer commercially available from GT-7080-S2 manufactured by high-speed railway of Taiwan, with reference to the method specified in GB/T1232.1-2000.

According to the rubber composition, compared with the existing butyl rubber, the butyl rubber has more excellent mixing performance, can effectively reduce the energy consumption of mixing under the condition that the Mooney viscosity is basically the same, and has more uniform additive dispersion. Compared with the existing butyl rubber, the butyl rubber has lower shear viscosity and extrusion swelling ratio, so that better processing fluidity can be obtained, the butyl rubber is more suitable for an injection process, and the prepared product has better dimensional stability.

According to the rubber composition of the present invention, the butyl rubber may be prepared by a process comprising the steps of: isobutene and isoprene are contacted with at least one grafting agent in at least one diluent under cationic polymerization conditions in the presence of at least one Lewis acid and at least one compound capable of donating a proton.

The amount of isobutylene and isoprene used in the process can be selected based on the desired composition of the butyl rubber. Generally, the isobutylene content may be 85 to 99% by weight, preferably 90 to 98% by weight, more preferably 93 to 97.5% by weight, based on the total amount of isobutylene and isoprene; the isoprene content may be 1 to 15 wt%, preferably 2 to 10 wt%, more preferably 2.5 to 7 wt%.

The grafting agent contains structural units derived from polymerizable structural units having a cationically polymerizable group and optionally also structural units derived from an aryl alkene. In the present invention, the "cationically polymerizable group" means a group having cationic polymerization activity, i.e., a group capable of reacting with isobutylene and/or a conjugated diene by a cationic polymerization mechanism under cationic polymerization reaction conditions, such as: the polymerizable structural unit can be a structural unit formed by 1, 2-polymerization and/or 3, 4-polymerization of conjugated diene, wherein a carbon-carbon double bond is a cation polymerizable group. In a preferred embodiment, the grafting agent contains structural units derived from a polymerizable group having a cationic polymerizable group and an arylalkene structural unit. In this preferred embodiment, the content of polymerizable structural units may be from 1 to 15 mol%, preferably from 2 to 14 mol%, more preferably from 2.5 to 12 mol%, based on the total amount of grafting agent. In this preferred embodiment, the content of the aryl olefin structural unit may be 20 to 98 mol%, preferably 30 to 97 mol%, more preferably 40 to 97 mol%, further preferably 50 to 97 mol%, and still further preferably 55 to 97 mol%, based on the total amount of the grafting agent. In the invention, the content of the aryl olefin structural unit in the grafting agent is determined by a nuclear magnetic resonance hydrogen spectrometry.

In the invention, the content of the structural units formed by the conjugated diene in a 1, 2-polymerization mode and a3, 4-polymerization mode is determined by using a nuclear magnetic resonance hydrogen spectrum.

The polymerizable structural unit having a cationically polymerizable group may be derived from a conjugated diene. The conjugated diene may specifically be a compound of formula II,

Preferably, the polymerizable building blocks having cationically polymerizable groups are derived from butadiene and/or isoprene.

The aryl alkene structural unit refers to a structural unit derived from an aryl alkene. The aryl alkene refers to a substance formed by substituting at least one hydrogen atom in alkene with an aryl group. Specifically, the aryl alkene may be a compound represented by formula I:

in the formula I, R₁Is C₆-C₂₀The aryl group of (2) may be specifically selected from phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-dodecylphenyl, 2, 4-di-n-butylphenyl, p-n-propylphenyl and 2, 4-diethylphenyl groups.

In the grafting agent, the aryl olefin structural unit is preferably a styrene structural unit derived from styrene.

In a preferred embodiment, the grafting agent contains polymerizable structural units derived from a conjugated diene, preferably butadiene and/or isoprene, and styrene structural units derived from styrene.

The grafting agent may have a weight average molecular weight of from 1 to 30 ten thousand, preferably from 2 to 20 ten thousand, more preferably from 5 to 18 ten thousand; molecular weight distribution index M_w/M_nMay be 1 to 2.5, preferably 1.1 to 2, more preferably 1.1 to 1.8. In the present invention, the weight average molecular weight of the grafting agent is measured by gel permeation chromatography, specifically by LC-20A liquid gel permeation chromatograph manufactured by Shimadzu corporation, and the chromatographic column is TSKgel G2000H_XL、TSKgel G3000H_XLAnd TSKgel G4000H_XLThe three columns are used together and provided with a differential detector. The mobile phase is tetrahydrofuran, and the flow rate is 1 mL/min; the concentration of the sample solution is 1mg/mL, and the sample injection amount is 200 mu L; the test temperature is 40 ℃; monodispersed polystyrene was used as a standard.

The grafting agent may be one or a combination of two or more selected from a styrene-butadiene copolymer and a pentylene-benzene copolymer, and is preferably a styrene-butadiene copolymer. The styrene-butadiene copolymer and the pentylene copolymer may be each a random copolymer, a block copolymer, or a mixture of a random copolymer and a block copolymer, and are not particularly limited.

The grafting agent may be added in an amount of 0.01 to 3% by weight based on isobutylene, preferably 0.1 to 2% by weight based on isobutylene, more preferably 0.15 to 1% by weight based on isobutylene, and still more preferably 0.2 to 0.8% by weight based on isobutylene.

The grafting agent is added into a polymerization reaction system together with polymerization monomers of isobutene and isoprene. The grafting agent can be dissolved in isoprene, then mixed with isobutene and a diluent, and the obtained mixture is added into a polymerization reaction system; it is also possible to mix the grafting agent with the diluent and then with isobutylene and isoprene and to add the resulting mixture to the polymerization system.

The Lewis acid is selected from a compound shown in a formula III,

A1R⁵ _nX^I _(3-n)(formula III).

In the formula III, n are R⁵Are the same or different and are each C₁-C₈Alkyl (including C)₁-C₈Straight chain alkyl of (2) and C₃-C₈Branched alkyl groups of (a). Specifically, n R⁵Each of which may be selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2, 3-dimethylbutyl, 2-dimethylbutyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2-dimethylpentyl, 2, 3-dimethylpentyl, 2, 4-dimethylpentyl, 3-dimethylpentyl, 3, 4-dimethylpentyl, 4-dimethylpentyl, 2, 3-dimethylpentyl, 3, 4-dimethylpentyl, 2, 3-dimethylpentyl, 2-dimethylpentyl, 3-dimethylpentyl, 2-dimethylpentyl, 3-dimethylpentyl, 2-dimethylpentyl, and, 2-ethylpentyl group, 3-ethylpentyl group, n-octyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 2-dimethylhexyl group, 2, 3-dimethylhexyl group, 2, 4-dimethylhexyl group, 2, 5-dimethylhexyl group, 3-dimethylhexyl group, 3, 4-dimethylhexyl group, 3, 5-dimethylhexyl group, 4-dimethylhexyl group, 4, 5-dimethylhexyl group, 5-dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-n-propylpentyl group and 2-isopropylpentyl group.

In the formula III, 3-n X¹Identical or different, are each one of the halogen radicals (such as-F, -Cl, -Br or-I), preferably-Cl.

In the formula III, n is 1, 2 or 3.

Specific examples of the lewis acid may include, but are not limited to, methylaluminum dichloride, ethylaluminum dichloride (EADC), n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, trimethylaluminum and triethylaluminum.

Preferably, the lewis acid is ethylaluminum dichloride and/or diethylaluminum chloride. More preferably, the lewis acid is ethyl aluminum dichloride.

The amount of the lewis acid may be selected according to the desired molecular weight of the butyl rubber. Generally, the molar ratio of the Lewis acid to the isobutylene can be 1: 500-5000, preferably 1: 1000-4000, more preferably 1: 1500-3500.

The compound capable of providing a proton is preferably a protonic acid, and specific examples of the protonic acid may include, but are not limited to: HCl, HF, HBr, H₂SO₄、H₂CO₃、H₃PO₄And HNO₃. Preferably, the compound capable of providing protons is HCl.

The molar ratio of the compound capable of donating a proton to the Lewis acid may be in the range of from 0.01 to 1: 1, preferably in the range of from 0.04 to 0.8: 1, more preferably in the range of from 0.08 to 0.2: 1, even more preferably in the range of from 0.08 to 0.15: 1.

The initiator system contains a Lewis acid represented by formula III and a protonic acid as a compound capable of providing protons.

The diluent may be selected from halogenated alkanes. The halogen atom in the haloalkane may be chlorine, bromine or fluorine, preferably chlorine or fluorine. The halogenated alkane is preferably C₁-C₁₀More preferably C₁-C₄The halogenated alkane of (4).

Specific examples of the diluent may include, but are not limited to, monofluoromethane, difluoromethane, trifluoromethane, carbon tetrafluoride, monochloromethane, dichloromethane, trichloromethane, carbon tetrachloride, monofluoroethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, carbon hexafluoride, monochloroethane, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, carbon hexachloride, monofluoropropane, difluoropropane, trifluoropropane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, heptafluoropropane, octafluoropropane, monochloropropane, dichloropropane, trichloropropane, tetrachloropropane, pentachloropropane, hexachloropropane, heptachloropropane, octachloropropane, monofluorobutane, difluorobutane, trifluorobutane, tetrafluorobutane, pentafluorobutane, hexafluorobutane, heptafluorobutane, octafluorobutane, nonafluorobutane, decafluorobutane, monochlorobutane, dichlorobutane, etc, Trichlorobutane, tetrachlorobutane, pentachlorobutane, hexachlorobutane, heptachlorobutane, octachlorobutane, nonachlorobutane and decachlorobutane.

The amount of the diluent may be conventionally selected. Generally, the diluent is used in an amount such that the total monomer (i.e., monoolefin and conjugated diolefin) concentration is from 1 to 50 weight percent, preferably from 5 to 45 weight percent, more preferably from 10 to 40 weight percent, and even more preferably from 20 to 35 weight percent.

The cationic polymerization conditions may be conventional in the art. In general, the polymerization reaction may be carried out at a temperature in the range of-120 ℃ to-50 ℃, preferably at a temperature in the range of-110 ℃ to-80 ℃, more preferably at a temperature in the range of-100 ℃ to-90 ℃.

According to the rubber composition of the present invention, the vulcanizing agent may be a substance capable of causing the butyl rubber to undergo a crosslinking reaction to form a three-dimensional network structure. According to the rubber composition of the present invention, the vulcanizing agent is preferably a phenol resin vulcanizing agent. The phenolic resin vulcanizing agent is preferably an alkyl phenolic resin (alkyl is positioned on a benzene ring of phenol) vulcanizing agent and/or halogenated alkyl phenolic resin vulcanizing agent, more preferably a p-alkyl phenolic resin vulcanizing agent and/or halogenated p-alkyl phenolic resin vulcanizing agent, and further preferably one or more than two of p-octyl phenolic resin, p-butyl phenolic resin, halogenated p-octyl phenolic resin and halogenated p-butyl phenolic resin, such as one or more than two of p-tert-octyl phenolic resin, p-tert-butyl phenolic resin and brominated p-tert-octyl phenolic resin.

According to the rubber composition of the present invention, the content of the methylol group in the phenolic resin vulcanizing agent may be 7 to 15% by weight. The halogen element may be contained in the halogenated alkyl phenol resin vulcanizing agent in an amount of 3 to 8% by weight.

The amount of the vulcanizing agent to be used is such that the rubber composition according to the present invention can be formed into a molded article having a certain strength, and can be appropriately selected according to the conventional knowledge in the art. Generally, the vulcanizing agent may be contained in an amount of 6 to 15 parts by weight, preferably 8 to 12 parts by weight, relative to 100 parts by weight of the butyl rubber.

The rubber composition according to the present invention preferably contains a halogen donor to promote resin vulcanization and shorten the vulcanization time. The halogen donor may be a halogen-containing polymer, and specific examples thereof may include, but are not limited to: one or a combination of two or more of chloroprene rubber, vinyl chloride elastomer, chlorinated butyl rubber and brominated butyl rubber, and chloroprene rubber is preferable.

The dosage of the halogen donor can be selected according to the dosage of the butyl rubber, so that the vulcanization speed of the butyl rubber can meet the requirement. Generally, the halogen donor may be contained in an amount of 0 to 8 parts by weight, preferably 2 to 8 parts by weight, and more preferably 3 to 5 parts by weight, relative to 100 parts by weight of the butyl rubber.

The rubber composition according to the present invention preferably contains a vulcanization accelerator to accelerate vulcanization. The vulcanization accelerator is preferably zinc oxide. The content of the vulcanization accelerator may be 1 to 8 parts by weight, preferably 2 to 5 parts by weight, relative to 100 parts by weight of the butyl rubber.

According to the rubber composition of the present invention, when the rubber composition contains zinc oxide, stearic acid is preferably further contained, and zinc oxide forms a zinc soap under the action of stearic acid, so that the solubility of zinc oxide in the rubber compound can be improved, and zinc oxide can be made more active. The stearic acid may be contained in an amount of 0.3 to 2 parts by weight, preferably 0.5 to 1.5 parts by weight, relative to 100 parts by weight of the butyl rubber.

According to the rubber composition of the present invention, the reinforcing agent is used to improve the mechanical properties of a product formed from the rubber composition, and at the same time, plays a role of filling to reduce the cost. The reinforcing agent can be one or more than two of carbon black, white carbon black and silicate. Preferably, the reinforcing agent is carbon black. The carbon black may be one or more of high-reinforcement type carbon black, medium-high reinforcement type carbon black and reinforcement type carbon black. Specific examples of the high-reinforcement type carbon black may include, but are not limited to, one or more of N110, N115, N121, N220, and N234, specific examples of the high-reinforcement type carbon black may include, but are not limited to, one or more of N326, N330, N339, N347, N351, and N375, specific examples of the medium-reinforcement type carbon black may include, but are not limited to, one or more of N539, N550, and N660, and specific examples of the reinforcement type carbon black may include, but are not limited to, one or more of N762 and N770. In a preferred embodiment, the reinforcing agent is N330 and N220, and the weight ratio of N330 to N220 is preferably 0.1-1: 1, more preferably 0.3-1: 1, even more preferably 0.6-1: 1, and even more preferably 0.8-1: 1.

According to the rubber composition of the present invention, the reinforcing agent may be contained in an amount of 40 to 70 parts by weight, preferably 50 to 60 parts by weight, based on 100 parts by weight of the butyl rubber.

The rubber composition according to the invention preferably further contains at least one softening agent to improve processability. The softener may be one or more of castor oil, paraffin oil and oleic acid. The amount of the processing aid may be selected according to its kind. For example: as the softener, the content of the softener may be 2 to 10 parts by weight, preferably 5 to 7 parts by weight, relative to 100 parts by weight of the butyl rubber.

The curing bladder prepared using the rubber composition of the first aspect of the present invention exhibits a significantly improved service life.

According to a fourth aspect of the present invention, there is provided a process for producing a curing bladder, which comprises mixing the respective components of the rubber composition according to the first aspect of the present invention and then molding the mixture.

According to the method of the fourth aspect of the present invention, the method of mixing the components of the rubber composition may comprise:

s1, optionally, mixing the butyl rubber and the halogen donor to obtain a first mixed rubber material;

s2, mixing the butyl rubber or the first mixed rubber material with a reinforcing agent, optional stearic acid and optional softening agent to obtain a second mixed rubber material;

s3, mixing the second mixed rubber compound with a vulcanizing agent and an optional vulcanization accelerator to obtain a third mixed rubber compound.

According to the production method of the fourth aspect of the present invention, in step S1, the butyl rubber and the halogen donor are kneaded at an initial temperature of 50 to 80 ℃, preferably 60 to 80 ℃ to obtain the first mixed compound, and the kneading time is preferably 20 to 80 seconds, more preferably 20 to 60 seconds.

In step S2, the butyl rubber or the first mixed rubber material is banburied with the reinforcing agent, the optional softener, and the optional stearic acid at a temperature of 130-.

In step S2, the roll gap for thin passing may be 2-4mm, and the temperature may be 35-45 ℃.

In step S3, the second mixed rubber material, the vulcanizing agent, and the optional vulcanization accelerator are subjected to internal mixing at an initial temperature of 35 to 45 ℃ for 2 to 5min to obtain a second internal mixed rubber material, and the second internal mixed rubber material is subjected to thin-passing to obtain a third mixed rubber material.

In step S3, the thin pass preferably includes a first thin pass and a second thin pass. The roll gap for carrying out the first thin passing is preferably 0.6-1mm, more preferably 0.7-0.9mm, and the temperature is preferably 35-45 ℃; the second thin pass is preferably carried out at a roll gap of 4 to 8mm, more preferably 5 to 7mm, and a temperature of 35 to 45 ℃. The number of first thin passes is preferably 5-7, such as 6. The number of second thin passes is preferably 3-5, preferably 4.

According to the preparation method of the fourth aspect of the invention, the third mixed rubber compound can be vulcanized and molded to obtain the vulcanized capsule. The vulcanization is preferably carried out at a temperature of from 190 ℃ to 210 ℃ and the vulcanization time is preferably from 30 to 60 minutes. The molding can be carried out in a screw type injection machine, and after vulcanization molding, the injection machine ejects the capsule out of the mold cavity to obtain the vulcanized capsule. When the screw type injection machine is used for injection molding, the temperature of the screw can be 70-80 ℃, and the pressure of the screw can be 12-18MPa, preferably 15-17 MPa. The vulcanization molding can be carried out at the temperature of 190-210 ℃, preferably 195-205 ℃, and the duration of the vulcanization molding can be 30-60min, preferably 45-55 min.

The vulcanized capsule prepared by the method of the invention has obviously improved service life, the service life reaches more than 600 times, and the ultimate service life reaches more than 650 times.

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

Preparation examples 1 to 8 are illustrative of the butyl rubber in the rubber composition according to the present invention and the preparation method thereof.

In the following preparation examples and preparation comparative examples, the molecular weight and molecular weight distribution information of butyl rubber were measured by a TDA302 type liquid gel permeation chromatograph manufactured by Viscotek corporation, USA, which is equipped with a differential detector, a light scattering detector and a viscosity detector, and the column was TSKgel GMH manufactured by TOSOH corporation_HR-L and TSKgel GMH_HR-H two columns in combination. The mobile phase is tetrahydrofuran, and the flow rate is 1.0 mL/min; the concentration of the sample solution is 0.8 mg/mL; the test temperature was 30 ℃.

In the following preparation examples and preparation comparative examples, the weight average molecular weight of the grafting agent was measured by gel permeation chromatography, specifically by LC-20A liquid gel permeation chromatograph manufactured by Shimadzu corporation, Japan, and the column was TSKgel G2000H_XL、TSKgel G3000H_XLAnd TSKgel G4000H_XLThe three columns are used together and provided with a differential detector. The mobile phase is tetrahydrofuran, and the flow rate is 1 mL/min; the concentration of the sample solution is 1mg/mL, and the sample injection amount is 200 mu L; the test temperature is 40 ℃; single distribution polystyrene was used as a standard.

In the following preparation examples and comparative preparations, AVANCE400 NMR spectrometer, commercially available from Bruker, Switzerland, at a magnetic field strength of 9.40 Tesla in CDCl, was used₃As solvent, TMS as internal standard, measuring the microstructure parameter of the grafting agent and the microstructure parameter of the prepared butyl rubber at room temperature (25 ℃),the microstructure parameters of the prepared butyl rubber include the total degree of unsaturation (i.e., the content of structural units formed from conjugated diene in the prepared butyl rubber), the content of structural units derived from isoprene, and the content of structural units derived from styrene.

In the following preparations and comparative preparations, Mooney viscosity and stress relaxation tests were carried out using a Mooney viscometer commercially available from GT-7080-S2, a high-speed railway company of Taiwan, China, and measured at 125 ℃ (1+8) using a large rotor according to the method of GB/T1232.1-2000, and the Mooney relaxation time was 120S.

In the following preparation examples and comparative preparations, the extrusion swell ratio of the rubber compound was measured by using a RH2000 type capillary rheometer manufactured by Malvern, UK at a temperature of 100 ℃, an aspect ratio of 16: 1 and a shear rate of 10 to 1000s^-1Is measured within the interval of (1).

In the following preparations and comparative preparations, the formulations of the mixes were referred to the SH/T1717-2008 standard formulation: 100g of butyl rubber, 50g of 8# carbon black, 1g of stearic acid, 3g of zinc oxide, 1.75g of sulfur and 1.0g of dithiotetramethylthiuram TMTD, and the total amount is 156.75 g. The mixing process comprises the following steps:

(1) feeding materials in a first section (BR1600 internal mixer at 50 ℃, 77 r/min), plasticating all butyl rubber for 0.5min, raising an upper top plug, adding stearic acid, zinc oxide and 8# carbon black, mixing for 0.5min, then lowering the upper top plug, mixing for 4.0min, and discharging rubber, wherein the temperature is controlled to be lower than 150 ℃;

(2) feeding materials in a two-stage (BR1600 internal mixer, 40 +/-5 ℃, 77 rpm), 1/2 master batch + S + TMTD +1/2 master batch, putting down an upper top plug in 0.5min, carrying out internal mixing for 2.5min, discharging rubber, controlling the temperature to be lower than 110 ℃, carrying out thin passing on an open mill for 6 times, carrying out the roll spacing of 0.8mm, carrying out the temperature of 40 ℃, carrying out sheet cutting in 2min, carrying out thin passing for 4 times, carrying out the roll spacing of 6mm, and carrying out the normal temperature for 1 min.

In the following preparation examples and preparation comparative examples, the physical and mechanical properties of the vulcanized rubber compound are tested by using a GT-AT-3000 type universal tensile machine produced by Taiwan high-speed railway, the tensile stress strain property of the rubber compound is tested according to GB/T528-containing power 2009, the tearing strength of the rubber compound is tested according to GB/T529-containing power 2008, and the Shore A hardness is tested according to GB/T531.1-2008.

Preparation examples 1 to 2

120mL of dichloromethane solution containing HCl (concentration is 0.009mol/L) and 6.7mL of normal hexane solution containing EADC (concentration is 0.9mo1/L) which are precooled to-80 ℃ are sequentially added into a 200mL cavel at the temperature of-80 ℃, and after uniform mixing, the obtained mixed solution is placed into a cold bath at the temperature of-80 ℃ for aging for 60min to obtain an initiator solution.

1100g of methyl chloride cooled to-60 ℃ was sequentially charged into a 2000mL glass reactor equipped with a high-speed stirrer (wherein K resin as a grafting agent, which is a product of Phillips, M, is listed in Table 1, and the amount of the grafting agent is dissolved in the methyl chloride)_w11.4 million, the content of butadiene in the K resin was 39.5 mol%, the content of a structural unit formed by 1, 2-polymerization of butadiene in the K resin was 4.6 mol%), 132g of isobutylene precooled to-60 ℃ and 6mL of isoprene precooled to-20 ℃, were uniformly mixed, and the cooling bath temperature was lowered to be in the range of-90 ℃ to-100 ℃. Then, 135mL of initiator solution was added to the reactor to initiate polymerization, and the temperature of the cold bath was controlled within the range of-90 ℃ to-100 ℃ during the reaction. After 30min of reaction, 10mL of a methanol solution containing 0.5% by weight of NaOH was added to the reactor to terminate the polymerization reaction. And (3) placing part of the obtained mixed solution in a hot water bath to remove the solvent, washing the obtained product with water, and drying the product in a vacuum oven at 60 ℃ to constant weight to obtain the butyl rubber. The results of the experiments are listed in tables 1 to 3.

Preparation of comparative example 1

Butyl rubber was prepared by the same method as in preparation example 1, except that no grafting agent was used.

Preparation of comparative example 2

Butyl rubber prepared by the same method as in preparation example 1, except that the initiator solution was prepared by the following method: weighing AlCl in an inert gas glove box₃390mg of the powder was put into a 200mL polymerization flask, and then refined CH was added₂Cl₂Solution 120mL (CH)₂Cl₂Water content in solution 10ppm), mixing well until AlCl₃After complete dissolution, the mixture is aged in a cooling bath at-80 ℃ for 60min to obtain an initiator solutionAnd (4) liquid.

TABLE 1

TABLE 2

¹: location of high molecular weight shoulder Log (Mw) Peak

TABLE 3

The results of preparation examples 1-2 confirm that the butyl rubber prepared by the method of the present invention has a larger area under the stress relaxation curve under the condition of similar Mooney viscosity, and thus has better cold flow resistance and can more effectively resist deformation in the transportation and storage processes; in addition, the butyl rubber prepared by the method has lower extrusion swelling effect (namely, low die-release expansion rate), and the prepared product has better dimensional stability.

FIG. 1 is a graph showing the die swell ratio of butyl rubber prepared in preparation examples 1 and 2 and preparation comparative example 1 as a function of shear rate, wherein the test was carried out at a temperature of 100 ℃ and with a die having an L/D of 16/1 at a temperature of 10 to 1000s^-1Measured over a range of shear rates.

As can be seen from FIG. 1, the butyl rubber prepared by the process of the present invention exhibits a lower die swell ratio (i.e., the butyl rubber according to the present invention has a lower die swell ratio) and thus a lower shrinkage, and the article has better dimensional stability, under substantially the same Mooney viscosity.

Test example 1

The butyl rubbers prepared in preparation examples 1 to 2 and preparation comparative examples 1 to 2 were each prepared into a compounded rubber, vulcanized (vulcanization temperature 150 ℃ C., vulcanization time 30nin), and physical and mechanical properties were measured, and the results of mechanical property experiments of the vulcanized rubber are shown in Table 4.

TABLE 4

	Preparation of comparative example 1	Preparation of comparative example 2	Preparation example 1	Preparation example 2
					Hardness (Shao's A)	64	64	65	66
Tensile strength/MPa	16.53	16.38	17.22	16.97
					100% stress at definite elongation/MPa	2.42	2.39	2.28	2.16
300% stress at definite elongation/MPa	9.17	9.17	8.55	8.28
					Elongation at break/%)	523	526	563	566
Permanent deformation/%)	30	31	30	29
					Tear Strength/kN/m	35	35	39	39

The results in Table 4 demonstrate that the butyl rubbers according to the invention have good overall mechanical properties, in particular show a higher elongation at break and a higher tear strength, and are suitable as curing bladders.

Preparation example 3

The continuous polymerization kettle with the capacity of 2t/h is filled with liquid ethylene at the temperature of-110 ℃ and is used for refrigerating through a tube bundle in the polymerization kettle, the polymerization reaction temperature in the kettle is controlled to be-95 ℃ to-100 ℃, two feeding materials are arranged at the bottom of the polymerization kettle and enter the kettle at the same time, and the feeding temperature is-95 ℃. Wherein the feed 1 is a monomer solution feed obtained by mixing isoprene dissolved with styrene-butadiene resin, methane chloride and isobutene; feed 2 is the initiator solution feed. The feeding was carried out according to the feed conditions of switch 2 in Table 5, the top of the polymerization vessel was the discharge of the slurry, no significant gel formation occurred during the polymerization, and the polymer slurry was coagulated in the degassing vessel and dried by after-treatment to give the butyl rubber according to the invention, the structure and the performance parameters of which are shown in Table 11.

Preparation of comparative example 3

Polymerization was carried out in the same manner as in preparation example 3, except that the feed was switched 1 as in Table 5 to obtain a butyl rubber (i.e., a commercially available butyl rubber having a trade name of IIR 1751) whose structure and performance parameters are set forth in Table 11.

TABLE 5

¹: available from Philips under the trade designation KR01, weight average molecular weight 114000, molecular weight distribution index (M)_w/M_z) 1.35, the content of a structural unit derived from butadiene in the styrene-butadiene resin was 39.5 mol%, and the content of a structural unit formed by 1, 2-polymerization of butadiene was 4.6 mol%.

Preparation example 4

Butyl rubber was prepared in the same manner as in preparation example 3, except that feeding was carried out under the conditions shown in Table 6, and no gel was formed during the polymerization. The butyl rubber according to the invention was prepared, the structure and the performance parameters of which are listed in Table 11.

TABLE 6

¹: the same as in preparation example 3.

Preparation example 5

Butyl rubber was prepared in the same manner as in preparation example 3, except that feeding was carried out under the conditions shown in Table 7, and no gel was formed during the polymerization. The butyl rubber according to the invention was prepared, the structure and the performance parameters of which are listed in Table 11.

TABLE 7

¹: commercially available from mao famous and under the trade designation SL-803, weight average molecular weight 124700, molecular weight distribution index of 1.38, content of structural units derived from butadiene in the styrene-butadiene resin of 36.2 mol%, and content of structural units formed by 1, 2-polymerization of butadiene of 4.8 mol%.

Preparation example 6

Butyl rubber was prepared in the same manner as in preparation example 3, except that feeding was carried out under the conditions shown in Table 8, and no gel was formed during the polymerization. The butyl rubbers according to the invention were prepared, the structure and the performance parameters of which are listed in Table 11.

TABLE 8

¹: available from philips under the trademark KR03, having a weight average molecular weight of 159400, a molecular weight distribution index of 1.68, a content of butadiene-derived structural units in the styrene-butadiene resin of 38.2 mol%, and a content of structural units formed by 1, 2-polymerization of butadiene of 4.6 mol%.

Preparation example 7

The continuous polymerization kettle with the capacity of 2t/h is filled with liquid ethylene at the temperature of-110 ℃ and is used for refrigerating through a tube bundle in the polymerization kettle, the polymerization reaction temperature in the kettle is controlled to be-95 ℃ to-100 ℃, two feeding materials are arranged at the bottom of the polymerization kettle and enter the kettle at the same time, and the feeding temperature is-95 ℃. Wherein the feed 1 is a monomer solution feed obtained by mixing isoprene dissolved with styrene-butadiene resin, methane chloride and isobutene; feed 2 is the initiator solution feed.

The feed conditions in Table 9 were followed, the top of the polymerization vessel was used for the slurry discharge, no significant gel formation occurred during the polymerization, and the polymer slurry was subjected to degassing vessel coagulation and post-treatment drying to give butyl rubber according to the invention, the structure and performance parameters of which are given in Table 11.

TABLE 9

¹: commercially available from basf under the designation GH62, weight average in amount 155800, in amount distribution index of 1.54, the content of structural units derived from butadiene in the styrene-butadiene resin was 42.4 mol%, and the content of structural units formed by 1, 2-polymerization of butadiene was 5.1 mol%.

Preparation example 8

The continuous polymerization kettle with the capacity of 2t/h is filled with liquid ethylene at the temperature of-110 ℃ and is used for refrigerating through a tube bundle in the polymerization kettle, the polymerization reaction temperature in the kettle is controlled to be-95 ℃ to-100 ℃, two feeding materials are arranged at the bottom of the polymerization kettle and enter the kettle at the same time, and the feeding temperature is-98 ℃. Wherein the feed 1 is a monomer solution feed obtained by mixing isoprene dissolved with styrene-butadiene resin, methane chloride and isobutene; feed 2 is the initiator solution feed.

The feed conditions in Table 10 were followed, the top of the polymerization vessel was used for the slurry discharge, no significant gel formation occurred during the polymerization, and the polymer slurry was subjected to degassing vessel coagulation and post-treatment drying to give butyl rubber according to the invention, the structure and performance parameters of which are given in Table 11.

Watch 10

1: the same as in preparation example 3.

Preparation of comparative example 4

Commercially available butyl rubber available from exxonmobil under the trade designation IIR 268.

FIGS. 2-4 are GPC graphs of butyl rubbers prepared in preparation examples 4, 6 and 8, respectively.

As can be seen from table 11 and fig. 2 to 4, the butyl rubber according to the present invention has a higher molecular weight.

Test example 2: extrusion processability

The butyl rubbers prepared in preparation examples 4 and 8 and the butyl rubbers prepared in preparation examples 3 and 4 were made into rubber compounds, and extrusion processability was measured, and the results of the test are shown in FIG. 5.

As can be seen from FIG. 5, the shear viscosity and the die swell ratio of the compound made of the butyl rubber according to the invention are significantly lower than those of the butyl rubbers prepared according to the preparation comparative examples 3 and 4, indicating that the butyl rubber according to the invention has better processing flowability, better dimensional stability of the article and lower shrinkage.

Test example 3: physical and mechanical properties of vulcanized rubber

Physical mechanical properties were tested after vulcanization (vulcanization temperature 150 ℃ C., vulcanization time 30min) of rubber mixtures prepared from the butyl rubbers prepared in preparation examples 3 to 8 and the butyl rubbers prepared in preparation examples 3 and 4, and the test results are shown in Table 12.

TABLE 12

From the results in table 12 it can be seen that the samples prepared from the butyl rubbers according to the invention have a good overall mechanical properties, in particular show a higher elongation at break and tear strength.

Examples 1 to 3 are for illustrating the rubber composition according to the present invention, the method for preparing the same, and the curing bladder prepared from the rubber composition.

The butyl rubbers used in examples 1-3 were prepared in the same manner as in preparation 3, except that the feed conditions were varied, as shown in Table 13, and the properties of the butyl rubbers used in examples 1-3 are shown in tables 14 and 15.

Watch 13

TABLE 14

Watch 15

Example 1

(1) 100 parts by weight of butyl rubber 1 and 3 parts by weight of chloroprene rubber (trade name SN232, available from Shanna synthetic rubber Co., Ltd.) were added to an internal mixer and mixed for 30 seconds at an initial temperature of 60 ℃; then, lifting the top bolt, opening a feeding gate, adding 25 parts by weight of carbon black with the brand number of N220 (purchased from Tianjin hundred million Borui chemical engineering Co., Ltd.), 25 parts by weight of carbon black with the brand number of N330 (purchased from Tianjin hundred million Borui chemical engineering Co., Ltd.), 6 parts by weight of castor oil (purchased from Beijing chemical reagent Co., Ltd. of national medicine group) and 0.5 part by weight of stearic acid (purchased from Beijing chemical reagent Co., Ltd. of national medicine group), closing the feeding gate, and pressing the top bolt; and banburying for 15min when the mixing temperature reaches 140 ℃, then lifting a top plug, opening the top plug to discharge rubber, thinly passing the rubber material on an open mill with the roll spacing of 3mm and the roll temperature of 40 +/-5 ℃ for three times, and standing the obtained rubber material for 3 h.

(2) Mixing the mixed glue obtained in the step (1) with 8 parts by weight of phenolic resin vulcanizing agent (SP-1045, product of Schenectady company in America) and 2 parts by weight of zinc oxide (purchased from Beijing chemical reagent Co., Ltd. of the national medicine group) in a mixing mill with the initial temperature of 40 ℃, and unloading the glue when the mixing time reaches 3 min; then the sizing material is thinly passed through an open mill with a roll gap of 0.8mm and a roll temperature of 40 +/-5 ℃ for six times, then the roll gap is adjusted to 6mm, the thinly passed is carried out for four times, and the obtained final sizing material is naturally cooled to room temperature (25 ℃). And (3) putting the final rubber material into a cold feeding pin type extruder, filtering and extruding the rubber strip for injection for vulcanization.

(3) Filling the rubber strip extruded in the step (2) into a screw of an injection machine, wherein the temperature of the screw is 70 ℃; extruding the rubber sheet by a screw rod, weighing by a metering pump, and putting the rubber sheet into a mold cavity for vulcanization molding, wherein the pressure of the screw rod is 16 MPa; the vulcanization temperature is 190 ℃, and the vulcanization time is 55 minutes; and after vulcanization, the injection press pushes the capsule out of the die cavity to obtain the vulcanized capsule.

The shore hardness of the vulcanized capsule prepared in the embodiment is 64HA, the tensile strength is 14.0MPa, the elongation at break is 740%, and the tear strength is 40.9N/mm; the prepared vulcanized capsule was aged with hot air (185 ℃ C.. times.24 h) and then tested to have a hardness of 85HA, a tensile strength of 7.9MPa and an elongation at break of 340%. The service life of the curing bladder was tested and determined to be 610 times and 698 times.

Comparative example 1

Comparative example 1 a curing bladder was prepared in the same manner as in example 1 except that the butyl rubber was the butyl rubber used in the preparation of comparative example 3.

The cured capsule prepared from comparative example 1 had a shore hardness of 64HA, a tensile strength of 13.3MPa, an elongation at break of 598%, and a tear strength of 38.9N/mm; the prepared vulcanized capsule was aged with hot air (185 ℃ C.. times.24 h) and then tested to have a hardness of 89HA, a tensile strength of 8.1MPa and an elongation at break of 345%. The service life of the curing bladder was tested and found to be 419 times and 621 times.

Comparative example 2

Comparative example 2 a curing bladder was prepared in the same manner as in example 1 except that the butyl rubber was the butyl rubber used in the preparation of comparative example 4.

The cured capsule prepared from comparative example 2 had a shore hardness of 66HA, a tensile strength of 14.0MPa, an elongation at break of 679%, and a tear strength of 42.5N/mm; the prepared vulcanized capsule was aged with hot air (185 ℃ C.. times.24 h) and then tested to have a hardness of 89HA, a tensile strength of 8.9MPa and an elongation at break of 385%. The service life of the curing capsule is tested, the service life is 589 times, and the limit life is 670 times.

Example 2

(1) 100 parts by weight of butyl rubber 2 and 5 parts by weight of chloroprene rubber (trade name SN232, available from Shanna synthetic rubber Co., Ltd.) were charged into an internal mixer and kneaded at an initial temperature of 80 ℃ for 60 seconds; then lifting a top bolt, opening a feeding gate, adding 30 parts by weight of carbon black with the brand number of N220 (purchased from Tianjin hundred million Borry chemical Co., Ltd.), 30 parts by weight of carbon black with the brand number of N330 (purchased from Tianjin hundred million Borry chemical Co., Ltd.), 5 parts by weight of castor oil (purchased from Beijing chemical reagent Co., Ltd. of the national medicine group) and 1 part by weight of stearic acid (purchased from Beijing chemical reagent Co., Ltd. of the national medicine group), closing the feeding gate, and pressing the top bolt; and when the mixing temperature reaches 150 ℃, banburying for 10min, then lifting a top bolt, opening the top bolt to discharge rubber, thinly passing the rubber material on an open mill with the roller spacing of 3mm and the roller temperature of 40 +/-5 ℃ for three times, and standing the obtained rubber material for 4 h.

(2) Mixing the mixed rubber obtained in the step (1), 5 parts by weight of zinc oxide (purchased from Beijing chemical reagent Co., Ltd., national medicine group) and 10 parts by weight of phenolic resin vulcanizing agent (product of Schenectady, USA) in a mixing mill with the initial temperature of 40 ℃, and unloading the rubber material when the mixing time reaches 4 min; then the sizing material is thinly passed through an open mill with a roll gap of 0.8mm and a roll temperature of 40 +/-5 ℃ for six times, then the roll gap is adjusted to 6mm, the thinly passed is carried out for four times, and the obtained final sizing material is naturally cooled to room temperature (25 ℃). And (3) putting the final rubber material into a cold feeding pin type extruder, filtering and extruding the rubber strip for injection for vulcanization.

(3) Filling the rubber strip extruded in the step (2) into a screw of an injection machine, wherein the temperature of the screw is 75 ℃; extruding the rubber sheet by a screw rod, weighing by a metering pump, and putting the rubber sheet into a mold cavity for vulcanization molding, wherein the pressure of the screw rod is 16 MPa; the vulcanization temperature is 198 ℃, and the vulcanization time is 47 minutes; and after vulcanization, the injection press pushes the capsule out of the die cavity to obtain the vulcanized capsule.

The shore hardness of the vulcanized capsule prepared in the embodiment is 66A, the tensile strength is 14.2MPa, the elongation at break is 750%, and the tear strength is 42.8N/mm; the prepared vulcanized capsule was aged with hot air (185 ℃ C.. times.24 h) and then tested to have a hardness of 86HA, a tensile strength of 8.7MPa and an elongation at break of 390%. The service life of the curing bladder was tested and it was determined that the service life was 615 times and the ultimate life was 730 times.

Example 3

(1) 100 parts by weight of butyl rubber 3 and 5 parts by weight of chloroprene rubber (trade name SN232, available from Shanna synthetic rubber Co., Ltd.) were charged into an internal mixer and kneaded at an initial temperature of 70 ℃ for 50 seconds; then, lifting a top bolt, opening a feeding gate, adding 25 parts by weight of carbon black with the brand number of N220 (purchased from Tianjin hundred million Borry chemical Co., Ltd.), 30 parts by weight of carbon black with the brand number of N330 (purchased from Tianjin hundred million Borry chemical Co., Ltd.), 7 parts by weight of castor oil (purchased from Beijing chemical reagent Co., Ltd. of the national medicine group) and 1.5 parts by weight of stearic acid (purchased from Beijing chemical reagent Co., Ltd. of the national medicine group), closing the feeding gate, and pressing the top bolt; banburying for 12min when the mixing temperature reaches 150 ℃, then lifting the top plug, and opening the bottom plug to discharge rubber; the sizing material is thinly passed through an open mill with the roll spacing of 3mm and the roll temperature of 40 +/-5 ℃ for three times, and the obtained sizing material is parked for 5 hours.

(2) Mixing the mixed rubber obtained in the step (1), 4 parts by weight of zinc oxide (purchased from Beijing chemical reagent Co., Ltd., national medicine group) and 12 parts by weight of phenolic resin vulcanizing agent (product of Schenectady, USA) in a mixing mill with the initial temperature of 40 ℃, and unloading the rubber material when the mixing time reaches 3 min; then the sizing material is thinly passed through an open mill with a roll gap of 0.8mm and a roll temperature of 40 +/-5 ℃ for six times, then the roll gap is adjusted to 6mm, the thinly passed is carried out for four times, and the obtained final sizing material is naturally cooled to room temperature (25 ℃). And (3) putting the final rubber material into a cold feeding pin type extruder, filtering and extruding the rubber strip for injection for vulcanization.

(3) Filling the rubber strip extruded in the step (2) into a screw of an injection machine, wherein the temperature of the screw is 80 ℃; extruding the rubber sheet by a screw rod, weighing by a metering pump, and putting the rubber sheet into a mold cavity for vulcanization molding, wherein the pressure of the screw rod is 16 MPa; the vulcanization temperature is 198 ℃, and the vulcanization time is 42 minutes; and after vulcanization, the injection press pushes the capsule out of the die cavity to obtain the vulcanized capsule.

The shore hardness of the vulcanized capsule prepared in the embodiment is 64HA, the tensile strength is 14.5MPa, the elongation at break is 740%, and the tear strength is 41.1N/mm; after the prepared vulcanized capsule is aged by hot air (185 ℃ for 24 hours), the vulcanized capsule is subjected to performance test, the hardness is 86HA, the tensile strength is 8.5MPa, and the elongation at break is 370 percent. The service life of the curing bladder was tested and determined to be 614 times and 715 times for ultimate life.

FIG. 6 is a photograph of the inside surface of the curing bladder prepared in example 1 after 589 uses. FIG. 7 is a photograph of the inner surface of the curing bladder prepared in comparative example 2 after 450 uses. As can be seen from FIGS. 6 and 7, the inner surface appearance of the curing bladder made from the rubber composition according to the present invention at 589 uses was comparable to or even better than the inner surface appearance of the curing bladder made from comparative example 2 at 450 times, indicating a greater increase in the service life of the curing bladder made from the composition of the present invention.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A rubber composition comprising a butyl rubber, a reinforcing agent and a vulcanizing agent, the vulcanizing agent being contained in an amount of 6 to 15 parts by weight and the reinforcing agent being contained in an amount of 40 to 70 parts by weight relative to 100 parts by weight of the butyl rubber, wherein the butyl rubber contains a structural unit derived from isobutylene, a structural unit derived from a conjugated diene, and optionally a structural unit derived from an aryl olefin, at least part of the conjugated diene being isoprene, the aryl olefin being selected from the group consisting of compounds represented by the formula I,

in the formula I, R₁Is C₆-C₂₀Aryl of (a);

in the butyl rubber, part of structural units derived from conjugated diene are used as grafting sites, so that part of molecular chains of the butyl rubber are grafted chains, and the rest of molecular chains of the butyl rubber are linear chains;

the butyl rubber has a peak molecular weight of 90 to 260 ten thousand, a butyl rubber content of log (MW) 6 or more of 30 to 80% by weight, and a content of a structural unit derived from a conjugated diene in the butyl rubber is 0.5 to 2.5 mol%.

2. The rubber composition according to claim 1, wherein the main chain of the graft chain contains a structural unit derived from a conjugated diene and a structural unit derived from an aryl olefin;

the branches of the grafted chain contain structural units derived from isobutylene as well as structural units derived from isoprene.

3. The rubber composition according to claim 2, wherein the main chain of the graft chain contains a structural unit derived from a conjugated diene and a structural unit derived from styrene.

4. The rubber composition according to claim 3, wherein the main chain of the graft chain is derived from a styrene-butadiene polymer and/or a pentylene-benzene polymer.

5. The rubber composition according to any one of claims 1 to 4, wherein the linear chain contains a structural unit derived from isobutylene and a structural unit derived from isoprene.

6. The rubber composition according to any one of claims 1 to 4, wherein the content of the structural unit derived from an aryl olefin is 0.01 to 3 mol% based on the total amount of the butyl rubber.

7. The rubber composition according to claim 6, wherein the content of the structural unit derived from the conjugated diene in the butyl rubber is 1.2 to 1.6 mol%; the content of structural units derived from an aryl olefin is from 0.05 to 0.6 mol%, based on the total amount of the butyl rubber.

8. The rubber composition according to claim 7, wherein the content of the structural unit derived from an aryl olefin is 0.1 to 0.5 mol% based on the total amount of the butyl rubber.

9. The rubber composition according to any one of claims 1 to 4, wherein the Mooney viscosity ML (1+8)125 ℃ of the butyl rubber is from 30 to 70.

10. The rubber composition according to claim 9, wherein the butyl rubber has a mooney viscosity ML (1+8)125 ℃ of 40-60.

11. The rubber composition according to any of claims 1 to 4, wherein the butyl rubber content of Log (MW) ≧ 6 is from 33 to 75% by weight.

12. The rubber composition of claim 11, wherein the butyl rubber content of log (mw) ≧ 6 is 35-70% by weight.

13. The rubber composition of claim 12, wherein the butyl rubber content of log (mw) ≧ 6 is 35-55 wt%.

14. The rubber composition according to any one of claims 1 to 4, wherein the butyl rubber has a peak molecular weight of 95 to 230 ten thousand.

15. The rubber composition of claim 14, wherein the butyl rubber has a peak molecular weight of 100 to 210 ten thousand.

16. The rubber composition of claim 15, wherein the butyl rubber has a peak molecular weight of 110 to 190 ten thousand.

17. The rubber composition of any of claims 1-4, wherein the butyl rubber has a bimodal distribution of molecular weights, and a high molecular weight shoulder having a Log (MW) value of between 6 and 7.5.

18. The rubber composition of claim 1, wherein the vulcanizing agent is a phenolic resin vulcanizing agent.

19. The rubber composition of claim 18, wherein the curative is an alkyl phenol-formaldehyde resin curative and/or a halogenated alkyl phenol-formaldehyde resin curative.

20. The rubber composition according to claim 19, wherein the vulcanizing agent is one or two or more of a p-octyl phenol resin, a p-butyl phenol resin, a halogenated p-octyl phenol resin, and a halogenated p-butyl phenol resin.

21. The rubber composition according to any one of claims 1 and 18 to 20, wherein the vulcanizing agent is contained in an amount of 8 to 12 parts by weight with respect to 100 parts by weight of the butyl rubber.

22. The rubber composition according to claim 1 or 18, further comprising at least one halogen donor.

23. The rubber composition of claim 22, wherein the halogen donor is a halogen-containing polymer.

24. The rubber composition according to claim 23, wherein the halogen donor is one or more of chloroprene rubber, vinyl chloride elastomer, chlorinated butyl rubber, and brominated butyl rubber.

25. The rubber composition according to claim 22, wherein the content of the halogen donor is 2 to 8 parts by weight with respect to 100 parts by weight of the butyl rubber.

26. The rubber composition according to claim 25, wherein the halogen donor is contained in an amount of 3 to 5 parts by weight relative to 100 parts by weight of the butyl rubber.

27. The rubber composition according to claim 1 or 18, wherein the rubber composition further contains a vulcanization accelerator.

28. The rubber composition of claim 27, wherein the vulcanization accelerator is zinc oxide.

29. The rubber composition according to claim 27, wherein the vulcanization accelerator is contained in an amount of 1 to 8 parts by weight relative to 100 parts by weight of the butyl rubber.

30. The rubber composition according to claim 29, wherein the vulcanization accelerator is contained in an amount of 2 to 5 parts by weight relative to 100 parts by weight of the butyl rubber.

31. The rubber composition according to claim 1 or 18, wherein the rubber composition further contains stearic acid.

32. The rubber composition according to claim 31, wherein the stearic acid is contained in an amount of 0.3 to 2 parts by weight relative to 100 parts by weight of the butyl rubber.

33. The rubber composition of claim 32, wherein the stearic acid is present in an amount of 0.5 to 1.5 parts by weight per 100 parts by weight of butyl rubber.

34. The rubber composition according to claim 1, wherein the reinforcing agent is one or two or more of carbon black, white carbon and silicate.

35. The rubber composition according to claim 1, wherein the reinforcing agent is carbon black.

36. The rubber composition according to claim 1, wherein the reinforcing agent is contained in an amount of 50 to 60 parts by weight relative to 100 parts by weight of the butyl rubber.

37. The rubber composition according to claim 1, further comprising at least one softening agent.

38. The rubber composition according to claim 37, wherein the softening agent is one or more of castor oil, paraffin oil, and oleic acid.

39. The rubber composition according to claim 37 or 38, wherein the softener is contained in an amount of 2 to 10 parts by weight relative to 100 parts by weight of the butyl rubber.

40. The rubber composition according to claim 39, wherein the softener is contained in an amount of 5 to 7 parts by weight, relative to 100 parts by weight of the butyl rubber.

41. Use of the rubber composition of any of claims 1-40 for the preparation of a curing bladder.

42. A curing bladder formed from the rubber composition of any of claims 1-40.

43. A process for producing a vulcanized capsule, which comprises mixing the respective components of the rubber composition according to any one of claims 1 to 40 and molding the mixture.

44. The method of claim 43, wherein the step of mixing the components of the rubber composition comprises:

45. The preparation method of claim 44, wherein in step S1, the butyl rubber and the halogen donor are mixed under the condition that the initial temperature is 50-80 ℃ to obtain the first mixed rubber compound, and the mixing time is 20-80 seconds.

46. The preparation method as claimed in claim 44, wherein in step S2, the butyl rubber or the first mixed rubber material is banburied with the reinforcing agent, the optional softener, and the optional stearic acid at 160 ℃ for 10-20min to obtain a banburied rubber material, and the banburied rubber material is subjected to thining to obtain a second mixed rubber material.

47. The production method according to claim 46, wherein in step S2, the roll gap at which the thin passing is performed is 2 to 4mm, and the temperature is 35 to 45 ℃.

48. The method of claim 44, wherein in step S3, the second compound mix, vulcanizing agent, and optional vulcanization accelerator are banburied for 2-5 minutes at an initial temperature of 35-45 ℃ to provide a second banburied compound, and the second banburied compound is tumbled to provide a third compound mix.

49. The production method according to claim 48, wherein the thin pass in step S3 includes a first thin pass and a second thin pass, the first thin pass is performed at a roll gap of 0.6 to 1mm and a temperature of 35 to 45 ℃, and the second thin pass is performed at a roll gap of 4 to 8mm and a temperature of 35 to 45 ℃.

50. The method of claim 44, curing the third compound mixture to form a curing bladder.

51. The production method according to claim 50, wherein the vulcanization molding is performed at a temperature of 190 ℃ to 210 ℃ for 30 to 60 minutes.

52. A curing bladder prepared by the method of any one of claims 43-51.