CN116003927A - Butyl rubber capable of being repeatedly processed and preparation method thereof - Google Patents
Butyl rubber capable of being repeatedly processed and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a butyl rubber capable of being repeatedly processed and a preparation method thereof, wherein the butyl rubber comprises the following raw materials in parts by weight: 200 parts of halogenated butyl rubber, 1-10 parts of phosphorus-containing nucleophile, 20-100 parts of filler, 30-40 parts of modified flame-retardant polymer, 1-5 parts of anti-aging agent, 3-6 parts of vulcanizing agent and 1-3 parts of vulcanizing auxiliary agent; the preparation method comprises the following specific steps: adding the halogenated butyl rubber and the phosphorus-containing nucleophilic reagent in the component amounts into an internal mixer, blending for 5-20min at 20-60 ℃, then adding the filler, the modified flame-retardant polymer, the anti-aging agent, the vulcanizing agent and the vulcanizing assistant, mixing for 5-20min at 50-80 ℃, feeding the materials into the internal mixer, and reacting for 5-30min at 80-160 ℃ in an oven to obtain the rubber sheet. Compared with the quaternary ammonium salt which is easy to generate Huffman elimination reaction, the thermal stability of the quaternary phosphonium salt is obviously increased, the side reaction is greatly reduced, and the retention rate of the mechanical property of the butyl rubber is obviously increased, so that the butyl rubber has higher practical application value.
Description
Technical Field
The invention belongs to the technical field of thermoplastic elastomers and preparation thereof, and particularly relates to a repeatedly-processable butyl rubber and a preparation method thereof.
Background
Butyl rubber is a type of copolymer rubber produced by cationic polymerization of isobutylene with small amounts of isoprene or other monomers. The tightness was excellent due to the spin effect of the methyl groups on both sides of the isobutylene unit. Butyl rubber and its halides are vulcanized and widely used for inner tubes, inner liners, etc. The vulcanization systems of butyl rubber and halogenated butyl rubber include sulfur, peroxide, phenolic resin, amine, zinc oxide, etc., and C-S or C-C covalent bonds are generated between molecular chains, and the vulcanization systems do not have reversible processability or thermoplasticity.
In recent years, with the increasing awareness of environmental protection and energy saving, with respect to conventional rubber, a reversible crosslinking vulcanization system has been intentionally developed so as to provide thermoplastic properties and reworkability. The prior art reports (slurry process for preparing poly (isobutylene-CO-p-methylstyrene) random copolymer and bromination and reversible vulcanization studies thereof, chemical engineering new type materials, volume 48, 7, pages 159-163) on the formation of ionomer crosslinked brominated isobutylene p-methylstyrene copolymer rubber using bis-tertiary amine compounds. However, the repeated processability of the quaternary ammonium salt ionic bond crosslinked butyl rubber is poor, and the tensile strength and the elongation at break after secondary processing are obviously reduced. This is because the quaternary ammonium salt formed by the tertiary amine compound and the halogenated butyl rubber has a Huffman elimination reaction of the quaternary ammonium salt in addition to a normal reversible dissociation reaction of the ionic bond under a high temperature environment at the time of repeated processing. This results in a decrease in the crosslink density and a significant deterioration in mechanical properties.
Butyl rubber is easy to burn, and a flame retardant is often added during production to improve the flame retardant property of the butyl rubber. The conventional flame retardant in rubber such as inorganic flame retardant of aluminum hydroxide, magnesium hydroxide, red phosphorus, and dittany, or organic flame retardant of phosphoric acid triphenol, and dimethyl phosphate, etc., while halogen flame retardant has been banned gradually because of environmental protection factor, but whether inorganic flame retardant or organic flame retardant is added into rubber material to increase its flame retardant property, but need to add more amount to reach good flame retardant property, but add more amount of flame retardant into rubber material, its compatibility and mechanical properties of rubber material can be worsened, such as tensile strength, impact strength, etc., and the time is longer that flame retardant is easy to ooze, the heat resistance is poor, unsuitable for rubber product of reprocessing, therefore, a premise of not influencing rubber material performance, can lasting keep flame retardant, for this application, still need to have good thermal stability in the course of reprocessing, have extensive practical application meaning.
Disclosure of Invention
The invention provides a novel repeatedly-processable butyl rubber and a preparation method thereof, and aims to solve the technical problems that a Huffman elimination reaction is easy to occur and the mechanical property is obviously deteriorated at the high temperature of repeated processing of a quaternary ammonium salt ionic crosslinking bond formed by the existing tertiary amine compound and halogenated butyl rubber.
The aim of the invention can be achieved by the following technical scheme:
the butyl rubber capable of being repeatedly processed comprises the following raw materials in parts by weight: 200 parts of halogenated butyl rubber, 1-10 parts of phosphorus-containing nucleophile, 20-100 parts of filler, 30-40 parts of modified flame-retardant polymer, 1-5 parts of anti-aging agent, 3-6 parts of vulcanizing agent and 1-3 parts of vulcanizing auxiliary agent.
Further, the halogenated butyl rubber may be selected from brominated butyl rubber, chlorinated butyl rubber, or brominated isobutylene para-methylstyrene copolymer.
Further, the phosphorus-containing nucleophile may be selected from compounds containing 2 and more trialkylphosphorus atoms in the molecule, including 1, 2-bis (diphenylphosphinomethyl) benzene, bis-diphenylphosphinomethane, 1, 3-bis (diphenylphosphinopropane), 1, 4-bis (diphenylphosphinobutane), 1, 5-bis (diphenylphosphinobutane), 1, 6-bis (diphenylphosphinohexane, 1, 7-bis (diphenylphosphinoheptane), 1, 8-bis (diphenylphosphinohexane), 1, 9-bis (diphenylphosphinohexane), 1, 10-bis (diphenylphosphinohexane), 1-tris (diphenylphosphinomethyl) ethane, 1, 2-bis (diethylphosphinohexane), 1, 2-bis (dimethylphosphinoethane, 1, 3-bis (di-isopropylphosphinohexane), 1, 4-bis (diisopropylphosphinohexane), 1, 4-bis (dimethylphosphinohexane), 1, 3-bis (di-tert-butylphosphine) propane, 1, 4-bis (di-tert-butylphosphine).
Further, the preparation method of the modified flame-retardant polymer comprises the following steps:
firstly, adding 4.3-4.5g DOPO, 4.9-5.5g 2,2' - [ [2- (allyloxy) -1, 3-phenylene ] di (methylene) ] di (ethylene oxide) and 0.8-1.0g azodiisobutyronitrile into a reaction bottle, introducing nitrogen, then adding 50ml-80ml solvent THF, continuously introducing 5-10min nitrogen for protection, reacting for 10-12h at 65-70 ℃, naturally cooling to room temperature after the reaction is finished, filtering, and adopting THF at 0-5 ℃ to wash filter cakes to obtain DOPO-dicycloxy intermediate;
and secondly, adding 3.0-3.5g of 4,4' - (dimethylsilanediyl) dibenzoic acid and 80-100ml of solvent cyclohexanol into a reaction bottle, starting heating to raise the temperature to 85-90 ℃, adding 0.5-0.8g of catalyst tetrabutylammonium bisulfate, then adding 4.6-5.0g of DOPO-dioxygen intermediate prepared in the first step, uniformly dividing into three parts, adding each part at a time interval of 10-15min, heating to 100-105 ℃ after the addition, preserving heat for 2-3h, adding 0.1-0.15g of polymerization inhibitor hydroquinone, stopping heating after reacting for 20-30min, and naturally cooling to room temperature to obtain the modified flame-retardant polymer.
Further, the filler is one of cellulose, barium sulfate, carbon black, clay, calcium carbonate, fly ash, silicon dioxide and talcum powder.
Further, the anti-aging agent is one of N-cyclohexyl-N '-phenyl-p-phenylenediamine and N, N' -di (2-naphthyl) p-phenylenediamine.
Further, the vulcanizing agent is one of 1, 3-bis (tert-butyl peroxyisopropyl) benzene and dicumyl peroxide.
Further, the vulcanization aid is zinc oxide.
A preparation method of a butyl rubber capable of being repeatedly processed comprises the following specific steps: 200 parts of halogenated butyl rubber and 1-10 parts of phosphorus-containing nucleophile are added into an internal mixer, blended for 5-20min at 20-60 ℃, then 20-100 parts of filler, 30-40 parts of modified flame-retardant polymer, 1-5 parts of anti-aging agent, 3-6 parts of vulcanizing agent and 1-3 parts of vulcanizing auxiliary agent are added, mixed for 5-20min at 50-80 ℃, and then the mixture is subjected to sheeting by an open mill, and reacted for 5-30min at 80-160 ℃ in an oven to obtain a film.
The invention has the beneficial effects that:
the invention uses a phosphorus-containing nucleophile and halogenated butyl rubber to form quaternary phosphonium salt ionic cross-links. In the high-temperature environment of repeated processing, compared with the quaternary ammonium salt which is easy to generate Huffman elimination reaction, the thermal stability of the quaternary phosphonium salt is obviously increased, and the side reaction is greatly reduced. During repeated processing, the retention rate of the mechanical property of the butyl rubber is obviously increased, so that the butyl rubber has higher practical application value.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of a modified flame retardant polymer;
FIG. 2 is a nuclear magnetic pattern of DOPO-bis-epoxy intermediates;
FIG. 3 is an infrared spectrum of a modified flame retardant polymer.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
200 g of brominated butyl rubber 2030, 5g of 1, 2-bis (diphenylphosphino) benzene are added into an internal mixer, blended for 8min at 50 ℃, 50g of filler barium sulfate, 35g of modified flame-retardant polymer, 2g of antioxidant N-cyclohexyl-N' -phenyl p-phenylenediamine, 4g of vulcanizing agent 1, 3-bis (tert-butylperoxyisopropyl) benzene and 1g of vulcanizing aid zinc oxide are added, mixed for 5-20min at 50 ℃, and then the mixture is discharged from an open mill and reacted for 25min at 110 ℃ in an oven to obtain a film.
Example 2
200 g of chlorinated butyl rubber, 10 g of 1, 3-bis (diphenylphosphine) propane are added into an internal mixer, blended for 10min at 60 ℃, 40g of filler clay, 30g of modified flame-retardant polymer, 4g of antioxidant N-cyclohexyl-N' -phenyl p-phenylenediamine, 3g of vulcanizing agent dicumyl peroxide and 2g of vulcanizing aid zinc oxide are added, mixed for 10min at 60 ℃, and the mixture is subjected to sheet feeding through an open mill and reacted for 20min at 130 ℃ in an oven to obtain a film.
Example 3
200 g of chlorinated butyl rubber, 7 g of 1, 2-bis (diphenylphosphino) benzene are added into an internal mixer, blended for 15min at 40 ℃, 70g of filler silicon dioxide, 40g of modified flame-retardant polymer, 5g of antioxidant N, N' -bis (2-naphthyl) p-phenylenediamine, 6g of vulcanizing agent 1, 3-bis (tert-butylperoxyisopropyl) benzene and 3g of vulcanizing aid zinc oxide are added, mixed for 5min at 80 ℃, and the mixture is discharged by an open mill and reacted for 25min at 100 ℃ in an oven to obtain a film.
Example 4
200 g of brominated butyl rubber 2030, 8g of 1, 1-tris (diphenylphosphinomethyl) ethane are added into an internal mixer, blended for 10min at 55 ℃, 80g of filler talcum powder, 33g of modified flame-retardant polymer, 3g of antioxidant N-cyclohexyl-N' -phenyl p-phenylenediamine, 4g of vulcanizing agent 1, 3-bis (tert-butylperoxyisopropyl) benzene and 1g of vulcanizing aid zinc oxide are added, mixed for 10min at 70 ℃, and the mixture is discharged from an open mill and reacted for 5min at 160 ℃ in an oven to obtain a film.
Comparative example 1
200 g of brominated butyl rubber 2030 and 5g of triethylenediamine are added into an internal mixer, blended for 8min at 50 ℃, 50g of filler barium sulfate, 35g of modified flame-retardant polymer, 2g of antioxidant N-cyclohexyl-N' -phenyl p-phenylenediamine, 4g of vulcanizing agent 1, 3-bis (tert-butylperoxyisopropyl) benzene and 1g of vulcanizing aid zinc oxide are added, mixed for 5-20min at 50 ℃, and then the mixture is subjected to sheet feeding by an open mill and reacted for 25min at 110 ℃ in an oven to obtain a film.
Comparative example 2
200 g of brominated isobutylene p-methylstyrene copolymer BIMS and 5g of bis (dimethylaminoethyl) ether are added into an internal mixer, blended for 8min at 50 ℃, 50g of filler barium sulfate, 35g of modified flame-retardant polymer, 2g of antioxidant N-cyclohexyl-N' -phenyl p-phenylenediamine, 4g of vulcanizing agent 1, 3-bis (tert-butylperoxyisopropyl) benzene and 1g of vulcanizing aid zinc oxide are added, mixed for 5-20min at 50 ℃, and then the mixture is discharged from an open mill and reacted for 25min at 110 ℃ in an oven to obtain a film.
Comparative example 3
200 g of brominated butyl rubber 2030, 5g of 1, 2-bis (diphenylphosphino) benzene are added into an internal mixer, blended for 8min at 50 ℃, 50g of filler barium sulfate, 35g of magnesium hydroxide, 2g of antioxidant N-cyclohexyl-N' -phenyl p-phenylenediamine, 4g of vulcanizing agent 1, 3-bis (tert-butylperoxy isopropyl) benzene and 1g of vulcanizing aid zinc oxide are added, mixed for 5-20min at 50 ℃, and the mixture is discharged by an open mill and reacted for 25min at 110 ℃ in an oven to obtain a film.
The preparation method of the modified flame retardant polymer in the embodiment comprises the following steps:
in a first step, 4.3g DOPO, 5.0g 2,2' - [ [2- (allyloxy) -1, 3-phenylene ] were charged into a reaction flask]Bis (methylene)]Bis (ethylene oxide) and 0.8g of azobisisobutyronitrile, nitrogen was purged, followed byAdding 80ml of solvent THF, continuously introducing nitrogen for protection for 5min, reacting for 12h at 70 ℃, naturally cooling to room temperature after the reaction is finished, filtering, and washing a filter cake by adopting the THF at 0-5 ℃ to obtain the DOPO-double epoxy intermediate, wherein the yield is 78%, and the melting process is as follows: 153.2-153.7; as shown in figure 2, the nuclear magnetic spectrum of the DOPO-double epoxy intermediate, 1 H NMR (500 MHz, CDCl 3 ) δ:8.51(d, 1H),8.39(d, 1H),8.20(d, 1H),8.08(t, 1H),7.93(t, 1H),7.71(t, 1H),7.23(m, 2H),7.11(dd, 3H),4.05-4.28(m, 4H),2.95(m, 1H),2.78(m, 1H),2.51-2.73(dd, 4H),2.46(dd, 4H),1.72 (m, 2H) 。
and secondly, adding 3.2g of 4,4' - (dimethylsilanediyl) dibenzoic acid and 100ml of solvent cyclohexanol into a reaction bottle, heating to 90 ℃, adding 0.5g of catalyst tetrabutylammonium bisulfate, adding 5.0g of DOPO-double epoxy intermediate prepared in the first step, uniformly dividing into three parts, adding for 15min at each time interval, heating to 105 ℃ after the addition, preserving heat for 2h, adding 0.1g of polymerization inhibitor, stopping heating after reacting for 30min, and naturally cooling to room temperature to obtain the modified flame-retardant polymer. FIG. 3 is an infrared spectrum of a modified flame retardant polymer, 3225cm -1 The stretching vibration peak of O-H is 3052cm -1 Is positioned at the stretching vibration peak of-H on benzene ring, 2926cm -1 at-CH 2 -a telescopic vibration peak 2894 of
Is a stretching vibration peak of-COO-at 1765, 1088cm -1 The stretching vibration peak of Si-C is shown.
Performance testing
The films of examples and comparative examples were compression molded to prepare a strong sheet for tensile testing, the strong sheet was sheared, compressed a second time, and the mechanical properties were tested, with reference to national standard GB/T528-2009, the results of which are given in table 1.
Table 1 results of performance testing of examples and comparative examples
The data of the examples prove that compared with tertiary amine ionic bond crosslinking agents, the halogenated butyl rubber which is crosslinked by adopting the polyphosphoric nucleophile ionic bond has outstanding tensile strength retention rate and elongation at break retention rate, thus having better practical use value; compared with the magnesium hydroxide flame retardant, the modified flame retardant polymer prepared by the application has good compatibility and does not reduce the mechanical properties of rubber materials.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (9)
1. A reworkable butyl rubber, characterized by: the material comprises the following raw materials in parts by weight: 200 parts of halogenated butyl rubber, 1-10 parts of phosphorus-containing nucleophile, 20-100 parts of filler, 30-40 parts of modified flame-retardant polymer, 1-5 parts of anti-aging agent, 3-6 parts of vulcanizing agent and 1-3 parts of vulcanizing auxiliary agent.
2. The reworkable butyl rubber as claimed in claim 1, wherein: the halogenated butyl rubber may be selected from brominated butyl rubber, chlorinated butyl rubber or brominated isobutylene para-methylstyrene copolymer.
3. The reworkable butyl rubber as claimed in claim 1, wherein: the phosphorus-containing nucleophile may be selected from compounds containing 2 and more trialkylphosphorus atoms in the molecule, including 1, 2-bis (diphenylphosphino) benzene, bis-diphenylphosphinomethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 5-bis (diphenylphosphino) pentane, 1, 6-bis (diphenylphosphino) hexane, 1, 7-bis (diphenylphosphino) heptane, 1, 8-bis (diphenylphosphino) octane, 1, 9-bis (diphenylphosphino) nonane, 1, 10-bis (diphenylphosphino) decane, 1-tris (diphenylphosphinomethyl) ethane, 1, 2-bis (diethylphosphino) ethane, 1, 2-bis (dimethylphosphine) ethane, 1, 3-bis (di-isopropylphosphino) propane, 1, 4-bis (diisopropylphosphino) butane, 1, 4-bis (dimethylphosphino) butane, 1, 3-bis (di-tert-butylphosphine) propane, 1, 4-bis (di-tert-butylphosphine) propane, and 1, 3-bis (di-butylphosphine).
4. The reworkable butyl rubber as claimed in claim 1, wherein: the preparation method of the modified flame-retardant polymer comprises the following steps:
firstly, adding 4.3-4.5g DOPO, 4.9-5.5g 2,2' - [ [2- (allyloxy) -1, 3-phenylene ] di (methylene) ] di (ethylene oxide) and 0.8-1.0g azodiisobutyronitrile into a reaction bottle, introducing nitrogen, then adding 50ml-80ml solvent THF, continuously introducing 5-10min nitrogen for protection, reacting for 10-12h at 65-70 ℃, naturally cooling to room temperature after the reaction is finished, filtering, and adopting THF at 0-5 ℃ to wash filter cakes to obtain DOPO-dicycloxy intermediate;
and secondly, adding 3.0-3.5g of 4,4' - (dimethylsilanediyl) dibenzoic acid and 80-100ml of solvent cyclohexanol into a reaction bottle, starting heating to raise the temperature to 85-90 ℃, adding 0.5-0.8g of catalyst tetrabutylammonium bisulfate, then adding 4.6-5.0g of DOPO-dioxygen intermediate prepared in the first step, uniformly dividing into three parts, adding each part at a time interval of 10-15min, heating to 100-105 ℃ after the addition, preserving heat for 2-3h, adding 0.1-0.15g of polymerization inhibitor hydroquinone, stopping heating after reacting for 20-30min, and naturally cooling to room temperature to obtain the modified flame-retardant polymer.
5. The reworkable butyl rubber as claimed in claim 1, wherein: the filler is one of cellulose, barium sulfate, carbon black, clay, calcium carbonate, fly ash, silicon dioxide and talcum powder.
6. The reworkable butyl rubber as claimed in claim 1, wherein: the anti-aging agent is one of N-cyclohexyl-N '-phenyl-p-phenylenediamine and N, N' -di (2-naphthyl) -p-phenylenediamine.
7. The reworkable butyl rubber as claimed in claim 1, wherein: the vulcanizing agent is one of 1, 3-bis (tert-butyl peroxyisopropyl) benzene and dicumyl peroxide.
8. The reworkable butyl rubber as claimed in claim 1, wherein: the vulcanization aid is zinc oxide.
9. A method of preparing a reworkable butyl rubber as claimed in any one of claims 1 to 8, wherein: the method comprises the following specific steps: 200 parts of halogenated butyl rubber and 1-10 parts of phosphorus-containing nucleophile are added into an internal mixer, blended for 5-20min at 20-60 ℃, then 20-100 parts of filler, 30-40 parts of modified flame-retardant polymer, 1-5 parts of anti-aging agent, 3-6 parts of vulcanizing agent and 1-3 parts of vulcanizing auxiliary agent are added, mixed for 5-20min at 50-80 ℃, and then the mixture is subjected to sheeting by an open mill, and reacted for 5-30min at 80-160 ℃ in an oven to obtain a film.
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| US20160108140A1 (en) * | 2012-12-20 | 2016-04-21 | Lanxess Butyl Pte. Ltd. | Ionomer comprising pendant vinyl groups and processes for preparing same |
| CN105705575A (en) * | 2013-09-09 | 2016-06-22 | 朗盛公司 | Filled butyl rubber ionomer compounds |
| US20180127537A1 (en) * | 2014-12-19 | 2018-05-10 | Henkel IP & Holding GmbH | Resins and compositions for high temperature applications |
| CN112048163A (en) * | 2020-08-22 | 2020-12-08 | 马鞍山吉祥光电科技有限公司 | Preparation method of impact-resistant street lamp shade material |
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2023
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004262963A (en) * | 2003-02-05 | 2004-09-24 | Jsr Corp | Flame-retardant rubber composition, rubber product and wire-coating material |
| JP2006052392A (en) * | 2004-07-13 | 2006-02-23 | Hitachi Chem Co Ltd | Epoxy resin molding material for encapsulation and electronic device |
| US20160108140A1 (en) * | 2012-12-20 | 2016-04-21 | Lanxess Butyl Pte. Ltd. | Ionomer comprising pendant vinyl groups and processes for preparing same |
| CN105008436A (en) * | 2012-12-26 | 2015-10-28 | 朗盛丁基私人有限公司 | Sulfur-free, zinc-free cure system for halobutyl and halogen containing polymers |
| CN105705575A (en) * | 2013-09-09 | 2016-06-22 | 朗盛公司 | Filled butyl rubber ionomer compounds |
| US20180127537A1 (en) * | 2014-12-19 | 2018-05-10 | Henkel IP & Holding GmbH | Resins and compositions for high temperature applications |
| CN112048163A (en) * | 2020-08-22 | 2020-12-08 | 马鞍山吉祥光电科技有限公司 | Preparation method of impact-resistant street lamp shade material |
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