CN113912794A - Itaconate bio-based elastomer with controllable sequence structure and adjustable cross-linking point distribution and preparation method thereof - Google Patents
Itaconate bio-based elastomer with controllable sequence structure and adjustable cross-linking point distribution and preparation method thereof Download PDFInfo
- Publication number
- CN113912794A CN113912794A CN202111119787.XA CN202111119787A CN113912794A CN 113912794 A CN113912794 A CN 113912794A CN 202111119787 A CN202111119787 A CN 202111119787A CN 113912794 A CN113912794 A CN 113912794A
- Authority
- CN
- China
- Prior art keywords
- monomer
- itaconate
- cross
- block
- linking point
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
An itaconate bio-based elastomer with controllable sequence structure and adjustable cross-linking point distribution and a preparation method thereof belong to the technical field of elastomers. The bio-based elastomer is prepared by feeding and polymerizing an itaconate monomer, a glass transition temperature adjusting monomer and a cross-linking point monomer according to a certain proportion, and is prepared by feeding and polymerizing each sequence of monomers or monomer mixtures in sections by adopting a soap-free emulsion polymerization method of forming micelles by using an amphiphilic RAFT (reversible addition-fragmentation chain transfer) reagent by adopting a reversible addition-fragmentation chain transfer (RAFT) polymerization method. The polymer has high molecular weight, low glass transition temperature, adjustable cross-linking point distribution and controllable sequence structure. The polymer may be composed of two, three or more blocks.
Description
The technical field is as follows:
the invention relates to an itaconate elastomer which is prepared by RAFT emulsion polymerization and has controllable sequence structure and adjustable cross-linking point distribution.
Technical background:
rubber has been developed for over 100 years and is one of three major polymeric materials. The rubber industry is one of the important basic industries of national economy in China. It not only provides daily and medical light rubber products which are indispensable to daily life for people, but also provides various rubber parts for heavy industries such as mining, traffic, building, machinery and electronics and emerging industries. The rubber industry has rapid development and fast generation, particularly rubber products in the non-tire field have faster development, the requirements on the rubber products are higher and higher, and the functional development is forward.
The rubber is divided into natural rubber and synthetic rubber. The natural rubber is prepared by extracting latex from plants such as rubber trees, rubber grasses and the like and then processing the latex; synthetic rubbers are obtained by polymerization of various monomers. The natural rubber has high elasticity and slight plasticity at normal temperature, and is crystallized and hardened at low temperature. Has better alkali resistance but does not resist strong acid. And because it contains unsaturated double bond, natural rubber is a substance with strong chemical reaction capability, and the ageing of rubber can be promoted by light, heat, ozone, radiation, flexion deformation, metals such as copper and manganese, and the non-ageing resistance is the fatal weakness of natural rubber. Due to the above disadvantages of natural rubber, synthetic rubber has been developed on the basis of natural rubber. Like butadiene rubber, the butadiene rubber has particularly excellent cold resistance, wear resistance and elasticity, and also has better aging resistance; the ethylene-propylene rubber is synthesized by taking ethylene and propylene as main raw materials, and has outstanding aging resistance, electrical insulation performance and ozone resistance. As with neoprene, neoprene has some corrosion resistance properties not found in natural rubber due to the presence of chlorine atoms. However, the sequence structure of these rubbers is not controllable, and people have no way to design the structure. On the basis of the above-mentioned raw material, the "third-generation rubber" is synthesized. Thermoplastic rubber, TPE for short, also known as thermoplastic elastomer, is a polymer material that exhibits rubber elasticity at room temperature and is plastic when heated. The rubber has the excellent performances of high elasticity, aging resistance and oil resistance of the traditional cross-linked vulcanized rubber, and has the characteristics of convenient processing and wide processing mode of common plastics. Styrene-butadiene-styrene block copolymers (SBS), which have partially replaced traditional rubbers; the use of the rubber composition in industrial rubber products such as rubberized fabric and rubber plate is also expanding. Block styrene polymers (SIS) of isoprene substituted butadiene are rapidly evolving, with about 90% being used in adhesives. Both SBS and SIS do not require conventional heat vulcanization and can be formed using standard thermoplastic processing equipment and processes such as extrusion, injection, blow molding, and the like. The biggest problem is poor heat resistance, and the service temperature of the thermoplastic elastomer cannot exceed 80 ℃. Meanwhile, the rubber has no better tensile property, weather resistance, oil resistance, wear resistance and the like than rubber. Therefore, an elastomer with a controllable sequence structure and adjustable cross-linking point distribution is needed to be invented, the controllable sequence structure means that people can design the structure according to self needs, and the adjustable cross-linking point distribution means that the cross-linking density and the cross-linking density distribution of a product obtained by subsequent processing are controllable. Thereby improving the strength and comprehensive mechanical property of the elastomer, and having better weather resistance, thermal aging resistance and corrosion resistance.
The invention constructs a main chain which is a carbon-carbon structure based on a bulk bio-based chemical itaconic acid, obtains a low glass transition temperature through copolymerization, contains a small amount of elastomer material which can crosslink active functional groups by non-sulfur, and prepares a bio-based elastomer material with required performance through RAFT emulsion polymerization. The invention adopts three monomers to carry out sequence controllable polymerization, and the cross-linking point is adjustable. The main chain of the polymer does not contain double bonds and can be vulcanized by adopting a non-sulfur vulcanization system.
The invention content is as follows:
the invention relates to an elastomer which is prepared by RAFT emulsion polymerization and has controllable sequence structure and adjustable distribution of cross-linking points, so that the elastomer has high molecular weight and low glass transition temperature.
An itaconate bio-based elastomer with a controllable sequence structure and adjustable cross-linking point distribution is prepared from itaconate monomer, monomer for regulating glass-transition temperature and cross-linking point monomer through sequential feeding according to the sequence of needed sequence structure and cross-linking point distribution, reversible addition-fragmentation chain transfer polymerization (RAFT) and emulsifier-free emulsion polymerization (HAS) in which amphiphilic RAFT reagent forms micelle.
The method specifically comprises the following steps:
closing the polymerization device, vacuumizing, and then filling argon to remove oxygen; adding deionized water, an RAFT reagent and a monomer into a reaction device, stirring and pre-emulsifying for 30-60min, preferably at a pre-emulsifying speed of 100-500 r/min, adding an initiator, reducing the rotating speed to 100-300 r/min, and heating to 40-80 ℃ for reaction; the total reaction time is 10-96 h; adding the RAFT reagent once, and adding the monomers and the initiator in batches for multiple times according to the required sequence structure and the distribution of cross-linking points;
the controllable sequence structure and the adjustable cross-linking point distribution mean that the corresponding sequence structure, the itaconate monomer corresponding to the cross-linking point, the monomer for adjusting the glass transition temperature and the cross-linking point monomer are added step by step or in batches for multiple times according to the required sequence structure and the cross-linking point distribution. If the sequence structure of the elastomer sequentially comprises an A block, a B block and a C block, wherein the cross-linking points are distributed on the corresponding A block or/and the B block or/and the C block, the addition sequence of the corresponding monomers is that an itaconate monomer corresponding to the A block, a monomer for adjusting the glass-transition temperature and a cross-linking point monomer are added for reaction, then an itaconate monomer corresponding to the B block, a monomer for adjusting the glass-transition temperature and a cross-linking point monomer are added for reaction, and an itaconate monomer corresponding to the C block, a monomer for adjusting the glass-transition temperature and a cross-linking point monomer are added for reaction. Wherein the A block, the B block and the C block are polymerized blocks of one or more of an itaconate monomer, a glass transition temperature adjusting monomer and a crosslinking point monomer, and the A block, the B block and the C block can be the same or different in pairs; or can be adjusted as desired, or different blocks can be added.
Wherein the total proportion of the monomers, the RAFT reagent, the initiator and the deionized water is as follows: monomer (100 parts by weight): RAFT reagent (0.5-10 parts by weight): initiator (0.005-0.05): deionized water (200 and 300 parts by weight).
(A) The molecular formula of the itaconate ester monomer is as follows:
wherein R is1、R2Is a hydrogen atom or C1-12Alkyl of R1、R2May be the same or different. The weight portion of the itaconate is 50-99 parts, preferably 50-80 parts. Too high a level of itaconate monomer, especially short side chain itaconate monomer, results in elastomers with high glass transition temperatures and brittle copolymer elastomers at room temperature.
(B) The glass transition temperature regulating monomer, homopolymer of which has lower glass transition temperature, is selected from n-propyl acrylate, n-butyl acrylate, 2-ethyl ethylhexyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, alkoxyethyl acrylate, etc. The glass transition temperature adjusting monomer is 0-49 parts by weight, preferably 30-49 parts by weight. When the amount of the component B is too large, the heat resistance is lowered, and when the amount of the component B is too small, the effect of improving the cold resistance of the itaconate ester elastomer is not good. For long side chain itaconate polymers, the monomer content to adjust the glass transition temperature may be zero.
(C) The crosslinking point monomer is vinyl monomer with crosslinkable functional group, such as amino, carboxyl, halogen, epoxy, etc., and may be one or more. The weight portion of the crosslinking point monomer is 1-10 parts, preferably 2-6 parts, and when the content of the crosslinking point monomer is too low, the crosslinking degree is not enough, and better mechanical properties cannot be obtained. Conversely, when the crosslinking site monomer content is too high, the degree of crosslinking tends to be too high.
The chlorine-containing vinyl monomer is selected from: chloroethyl vinyl ether, chloroethyl acrylate, vinylbenzyl chloride, vinyl chloroacetate, allyl chloroacetate and chloromethyl styrene.
The epoxy group-containing vinyl monomer is selected from: glycidyl acrylate, glycidyl methacrylate, diglycidyl tricarboxylate, triglycidyl tricarboxylate, propenyl glycidyl ether, methacryl glycidyl ether.
The carboxyl group-containing vinyl monomer is selected from: acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic acid monoester.
The amino group-containing vinyl monomer is selected from: acrylamide, dimethylaminoethyl methacrylate.
The initiator is azobisisobutyronitrile, azobisisoheptanide, 4, 4' -azo (4-dicyano valeric acid), azobisisobutyrimidazoline hydrochloride, azobisisopropylimidazoline, dibenzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide or di-tert-butyl peroxide; the initiator can be added in one portion or in each case in the corresponding block reaction, as desired.
The chemical structural general formula of the amphiphilic macromolecule reversible addition fragmentation chain transfer reagent is as follows:
AA is an acrylic acid unit, a methacrylic acid unit, St is a styrene unit, R' is alkyl with carbon number from four to twelve, R is isopropyl acid group, acetic acid group, 2-cyanoacetic acid group, 2-amino acetic acid group and 2-methyl propionic acid group, wherein m and n are average polymerization degrees of the styrene unit and the (methyl) acrylic acid unit respectively, m is 3-7, and n is 20-60.
The itaconate elastomer material with controllable sequence structure and adjustable cross-linking point distribution is characterized in that raw materials of the itaconate bio-based elastomer at least comprise the itaconate bio-based elastomer and a vinyl monomer capable of providing a cross-linking functional group. When the chlorine-containing vinyl monomer is used as a crosslinking point monomer for copolymerization, the vulcanizing agent can be an amine compound, a triazine compound and the like; when the epoxy vinyl monomer is used as a crosslinking point monomer for copolymerization, the vulcanizing agent can be polyamine, carboxylic acid ammonium salt, quaternary ammonium salt/urea vulcanizing agent and the like; when a carboxyl group-containing vinyl monomer is copolymerized as a crosslinking point monomer, the vulcanizing agent may be a hexamethylenediamine vulcanizing agent, and diphenylguanidine is usually used as a vulcanization accelerator; when the amino vinyl-containing monomer is copolymerized as a crosslinking point monomer, the vulcanizing agent may be adipic acid.
The invention has the following effects: the raw materials are bio-based elastomer materials obtained by taking bio-based chemical itaconate obtained by fermenting and esterifying biological resources as a main monomer, and polymerizing the bio-based chemical itaconate, a glass transition temperature monomer and a monomer capable of providing a crosslinking point through an RAFT emulsion taking an amphiphilic RAFT reagent as an emulsifier. The bio-based elastomer can be a two-block, three-block or multi-block structure, the sequence structure of the bio-based elastomer is controllable, the distribution of cross-linking points is adjustable, the glass transition temperature is low, and non-sulfur cross-linking can be adopted. The glass transition temperature of the copolymer can be adjusted by changing the monomer proportion, the crosslinking density of the polymer can be adjusted by adjusting the content of the crosslinking point monomer, and meanwhile, the distribution of the crosslinking point monomer can be adjusted by changing the position cross of the crosslinking point monomer, so that the distribution of the crosslinking density can be adjusted.
The specific implementation case is as follows:
for better understanding of the present invention, the following examples are given to illustrate the technical solution of the present invention, but the present invention is not limited thereto.
The RAFT agent used in the present invention can be selected according to the sequence structure of the multi-block polymer and the kind of the monomer, and the range of the selection is as defined in claim 3. Three RAFT agents were used in the following examples and the synthesis procedure was as follows.
The synthesis process of the small molecule RAFT reagent a (R group is an isopropenyl group) is as follows: in a 100mL three-necked flask equipped with a stirrer, 0.5g of NaOH (12.5mmol) was added to a mixed solution of dodecanethiol (3.0m L, 2.5g, 12.5mmol), acetone (40mL), distilled water (5mL) and tetrapropylammonium bromide (0.27g, 0.10mmol) with stirring at room temperature. To dissolve completely, 0.75m L carbon disulfide (0.95g, 12.5mmol) was added to the solution with stirring in an ice bath. 1.91g 2-Bromopropionic acid (1.13mL, 12.5mmol) was added to the mixture and the reaction stirred at room temperature for 8 h. The solvent was removed by rotary evaporation to 1/4 of the original volume of the mixed solution. The residue was acidified by adding 50mL of dilute hydrochloric acid to a 250mL beaker, and diluted with 150mL of distilled water. The precipitate was collected and recrystallized in petroleum ether and hexane to give trithiocarbonate.
The synthesis process of the small molecule RAFT reagent b (R group is 2-methyl propionic acid group) is as follows: 12mL of dodecanethiol (10.095g, 0.05mol), 30.7mL of acetone (24.05g, 0.41mol) and Aliquot 336 (trioctylmethylammonium chloride, 0.81g, 0.002 mol) were mixed in a flask and cooled to 10 ℃ under nitrogen. Then 50% sodium hydroxide solution (4.19g,0.0525mol) is added, the dropwise addition is controlled to be over 20min, and the reaction is continuously stirred for 15 min. The solution was milky white. 3mL of carbon disulfide (3.8025g,0.05mol) dissolved in 6.5mL of acetone (5.045g,0.86mol) was added to the flask at a rate. After 10min, chloroform (8.91g,0.075mol) was added to the mixture in portions. 50% sodium hydroxide solution (20g,0.25mol) was added over 30 min. The reaction was left at room temperature overnight. The combined solution was poured into a beaker and 75mL of water was added, along with 12.5mL of concentrated HCl acidified aqueous solution. Vigorous stirring in a fume hood helps to evaporate the acetone. The solid was collected on a buchner funnel. Insoluble matter was dissolved in 100mL of isopropanol. The isopropanol filtrate was concentrated and dried, and the resulting solid was recrystallized from n-hexane to give 9.2g of yellow crystals. It is S-1-dodecyl-S' - (alpha, alpha "-dimethyl-alpha" -acetic acid) trithiocarbonate.
Amphiphilic RAFT Agent A (AA)20-St7Macro-RAFT, R is an isopropanoyl) as follows: 1.500g (4.25mmol) of small molecule RAFT agent a, 0.1g (3.57X 10)-4mol) of V501 initiator, 6.200g (8.57X 10)-2mol) of acrylic acid and 40g of 1, 4-dioxane were placed in a flask, nitrogen was introduced to remove oxygen for 30min, the reaction was carried out at 80 ℃ for 2.5 hours, the reaction was cooled to room temperature, and then 6.500g of styrene (4.29X 10) was added-2mol) and 0.1g (3.57X 10)-4mol) of V501 initiator, reacting at 80 ℃ for 13 hours, and precipitating the solution after the reaction in cyclohexane to obtain the product.
Amphiphilic RAFT agent B (AA)20-St5Macro-RAFT, R is an isopropanoyl) as follows: 1.500g (4.25mmol) of small molecule RAFT agent a, 0.1g (3.57X 10)-4mol) of V501 initiator, 6.200g (8.57X 10)-2mol) of acrylic acid and 40g of 1, 4-dioxane were placed in a flask, nitrogen was introduced to remove oxygen for 30min, the reaction was carried out at 80 ℃ for 2.5 hours, the reaction was cooled to room temperature, and 4.450g of styrene (4.29X 10) were then added-2mol) and 0.1g (3.57X 10)-4mol) of V501 initiator at 80 ℃ for 13 hours, as described aboveThe solution after the reaction was precipitated in cyclohexane to give the product.
Amphiphilic RAFT agent C (AA)20-St7Macro-RAFT, R is 2-methyl propionate) as follows: 1.500g (4.25mmol) of small molecule RAFT agent b, 0.1g (3.57X 10)-4mol) of V501 initiator, 6.200g (8.57X 10)-2mol) of acrylic acid and 40g of 1, 4-dioxane were placed in a flask, nitrogen was introduced to remove oxygen for 30min, the reaction was carried out at 80 ℃ for 2.5 hours, the reaction was cooled to room temperature, and then 6.500g of styrene (4.29X 10) was added-2mol) and 0.1g (3.57X 10)-4mol) of V501 initiator, reacting at 80 ℃ for 13 hours, and precipitating the solution after the reaction in cyclohexane to obtain the product.
Example 1
Taking the synthesis of a triblock polymer as an example, the sequence order of the three segments is a dibutyl itaconate-glycidyl methacrylate segment, a dibutyl itaconate-n-butyl acrylate segment and a dibutyl itaconate-glycidyl methacrylate segment. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St7Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 10g of dibutyl itaconate and 1g of crosslinking point monomer glycidyl methacrylate, adding the mixture and a water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 4 hours; then adding 30g of dibutyl itaconate and 48g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 15 hours; then 10g of dibutyl itaconate and 1g of cross-linking point monomer glycidyl methacrylate are added, 0.02g of initiator is added, polymerization reaction is carried out for 4 hours, cooling and discharging are carried out, 1% calcium chloride aqueous solution is adopted for flocculation, and drying is carried out.
Example 2
To synthesize triblock polymersFor example, the sequence order of these three segments is a dibutyl itaconate-glycidyl methacrylate segment, a dibutyl itaconate-n-butyl acrylate segment, and a dibutyl itaconate-glycidyl methacrylate segment. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St5Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 30g of dibutyl itaconate and 1g of crosslinking point monomer glycidyl methacrylate, adding the mixture and a water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 8 hours; then adding 30g of dibutyl itaconate and 8g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 9 hours; then 30g of dibutyl itaconate and 1g of cross-linking point monomer glycidyl methacrylate are added, 0.02g of initiator is added, polymerization reaction is carried out for 8 hours, cooling and discharging are carried out, 1% calcium chloride aqueous solution is adopted for flocculation, and drying is carried out.
Example 3
Taking the synthesis of the triblock polymer as an example, the sequence order of the three segments is a dibutyl itaconate-glycidyl methacrylate segment, a dibutyl itaconate segment and a dibutyl itaconate-glycidyl methacrylate segment. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St7Macro-RAFT, R is 2-methylpropanoyl) reversible addition fragmentation chain transfer agent is added into 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 30g of dibutyl itaconate and 1g of crosslinking point monomer glycidyl methacrylate, adding the mixture and a water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. In this, the reaction is mechanically stirredThe rotating speed of (2) is 300 r/min. Carrying out polymerization reaction for 8 hours; then adding 30g of dibutyl itaconate and 8g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 9 hours; then 30g of dibutyl itaconate and 1g of cross-linking point monomer glycidyl methacrylate are added, 0.02g of initiator is added, polymerization reaction is carried out for 8 hours, cooling and discharging are carried out, 1% calcium chloride aqueous solution is adopted for flocculation, and drying is carried out.
Example 4
The three segments are sequentially an itaconic acid dibutyl ester-methacrylic acid glycidyl ester segment, an itaconic acid dibutyl ester-acrylic acid n-butyl ester segment and an itaconic acid dibutyl ester-methacrylic acid glycidyl ester segment. 2.00g of amphiphilic macromolecules (the structure of the amphiphilic RAFT reagent is AA)20-St7Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 10g of dibutyl itaconate and 1g of crosslinking point monomer glycidyl methacrylate, adding the mixture and a water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 4 hours; then adding 30g of dibutyl itaconate and 48g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 15 hours; then 10g of dibutyl itaconate and 1g of cross-linking point monomer glycidyl methacrylate are added, 0.02g of initiator is added, polymerization reaction is carried out for 4 hours, cooling and discharging are carried out, 1% calcium chloride aqueous solution is adopted for flocculation, and drying is carried out.
Example 5
The three sections are sequentially an itaconic acid diethyl ester-glycidyl methacrylate section, an itaconic acid diethyl ester-n-butyl acrylate section and an itaconic acid diethyl ester-glycidyl methacrylate section. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St7Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 10g of diethyl itaconate and 1g of crosslinking point monomer glycidyl methacrylate, adding the mixture and a water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 4 hours; then adding 30g of diethyl itaconate and 48g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 15 hours; then 10g of diethyl itaconate and 1g of cross-linking point monomer glycidyl methacrylate are added, 0.02g of initiator is added, polymerization reaction is carried out for 4 hours, cooling and discharging are carried out, 1% calcium chloride aqueous solution is adopted for flocculation, and drying is carried out.
Example 6
The three segments are sequentially an itaconic acid dibutyl ester-methacrylic acid glycidyl ester segment, an itaconic acid dibutyl ester-acrylic acid n-butyl ester segment and an itaconic acid dibutyl ester-methacrylic acid glycidyl ester segment. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St7Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 10g of dibutyl itaconate and 1.5g of cross-linking point monomer glycidyl methacrylate, adding the mixture and a water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 4 hours; then adding 30g of dibutyl itaconate and 47g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 15 hours; then 10g of dibutyl itaconate and 1.5g of crosslinking point monomer are addedAnd adding 0.02g of initiator into glycidyl methacrylate, carrying out polymerization reaction for 4 hours, cooling and discharging, flocculating by adopting 1% calcium chloride aqueous solution, and drying.
Example 7
The three segments are sequentially itaconic acid dibutyl ester-acrylic acid n-butyl ester segment, acrylic acid n-butyl ester-methacrylic acid glycidyl ester segment and itaconic acid dibutyl ester-acrylic acid n-butyl ester segment. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St7Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 25g of dibutyl itaconate and 10g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding the mixture and a water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 8 hours; then 28g of dibutyl itaconate and 2g of cross-linking point monomer glycidyl methacrylate are added, 0.02g of initiator is added, and polymerization reaction is carried out for 8 hours; then adding 25g of dibutyl itaconate and 10g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, carrying out polymerization reaction for 8 hours, cooling and discharging, flocculating by adopting 1% calcium chloride aqueous solution, and drying.
Example 8
The triblock polymer is synthesized, and the sequence order of the three segments is an itaconic dibutyl-chloroethyl vinyl ether segment, an itaconic dibutyl-n-butyl acrylate segment and an itaconic dibutyl-chloroethyl vinyl ether segment. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St7Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 10g of dibutyl itaconate and 1g of chloroethyl vinyl ether as a crosslinking point monomer, adding the mixture and the water phase into a reaction kettle together, and carrying out mechanical processingPre-emulsifying for 1 hour at the rotation speed of 300r/min by mechanical stirring, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 4 hours; then adding 30g of dibutyl itaconate and 48g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 15 hours; then 10g of dibutyl itaconate and 1g of cross-linking point monomer chloroethyl vinyl ether are added, 0.02g of initiator is added, polymerization reaction is carried out for 4 hours, cooling and discharging are carried out, 1% calcium chloride aqueous solution is adopted for flocculation, and drying is carried out.
Example 9
Taking the synthesis of a four-block polymer as an example, the sequence order of the four blocks is itaconic dibutyl ester-glycidyl methacrylate block, itaconic dibutyl ester-n-butyl acrylate block, itaconic dibutyl ester-glycidyl methacrylate block, itaconic dibutyl ester-n-butyl acrylate block. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St7Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 10g of dibutyl itaconate and 1g of crosslinking point monomer glycidyl methacrylate, adding the mixture and a water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 4 hours; then adding 15g of dibutyl itaconate and 24g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 9 hours; then 10g of dibutyl itaconate and 1g of crosslinking point monomer glycidyl methacrylate are added, 0.02g of initiator is added for polymerization reaction for 4 hours, 15g of dibutyl itaconate and 24g of monomer n-butyl acrylate for adjusting the glass transition temperature are added, 0.02g of initiator is added for polymerization reaction for 9 hours, cooling and discharging are carried out, 1% of calcium chloride is adoptedFlocculating the aqueous solution and drying.
Example 10
Taking the synthesis of a four-block polymer as an example, the sequence order of the four blocks is a dibutyl itaconate-glycidyl methacrylate block, a n-butyl acrylate block, a dibutyl itaconate-glycidyl methacrylate block, and n-butyl acrylate. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St7Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 25g of dibutyl itaconate and 1g of crosslinking point monomer glycidyl methacrylate, adding the mixture and a water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 5 hours; then 24g of monomer n-butyl acrylate for adjusting the glass transition temperature is added, 0.02g of initiator is added, and the polymerization reaction is carried out for 5 hours; then adding 25g of dibutyl itaconate and 1g of crosslinking point monomer glycidyl methacrylate, adding 0.02g of initiator, carrying out polymerization reaction for 5 hours, adding 24g of monomer n-butyl acrylate for adjusting glass transition temperature, adding 0.02g of initiator, carrying out polymerization reaction for 10 hours, cooling and discharging, flocculating by adopting 1% calcium chloride aqueous solution, and drying.
Example 11
The five-block polymer is synthesized, and the sequence order of the five blocks is an itaconic acid dibutyl ester-methacrylic acid glycidyl ester segment, itaconic acid dibutyl ester-n-butyl acrylate segment, itaconic acid dibutyl ester-methacrylic acid glycidyl ester segment, itaconic acid dibutyl ester-n-butyl acrylate segment itaconic acid dibutyl ester-methacrylic acid glycidyl ester segment. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St7Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; 10g of dibutyl itaconate and 1g of crosslinking point monomer were addedAnd (2) adding the mixture and the water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes in the stirring process, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 4 hours; then adding 15g of dibutyl itaconate and 24g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 8 hours; then adding 10g of dibutyl itaconate and 0.5g of crosslinking point monomer glycidyl methacrylate, adding 0.02g of initiator, carrying out polymerization reaction for 4 hours, then adding 15g of dibutyl itaconate and 24g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 8 hours; then 10g of dibutyl itaconate and 0.5g of cross-linking point monomer glycidyl methacrylate are added, 0.02g of initiator is added, polymerization reaction is carried out for 4 hours, cooling and discharging are carried out, 1% calcium chloride aqueous solution is adopted for flocculation, and drying is carried out.
Example 12
The six-block polymer is synthesized, and the sequence order of the six-block polymer is an itaconic acid dibutyl ester-methacrylic acid glycidyl ester segment, itaconic acid dibutyl ester-n-butyl acrylate segment, itaconic acid dibutyl ester-methacrylic acid glycidyl ester segment, itaconic acid dibutyl ester-n-butyl acrylate segment itaconic acid dibutyl ester-methacrylic acid glycidyl ester segment. 1.50g of amphiphilic macromolecules (the structure of amphiphilic RAFT reagent is AA)20-St5Macro-RAFT, R is an isopropanolate group) reversible addition fragmentation chain transfer agent is added to 200g of water by weight and stirred; forming an aqueous phase; adding a mixture of 10g of dibutyl itaconate and 1g of crosslinking point monomer glycidyl methacrylate, adding the mixture and a water phase into a reaction kettle, pre-emulsifying for 1 hour at the mechanical stirring speed of 300r/min, introducing argon to remove oxygen for 30 minutes during stirring, heating to 70 ℃, introducing argon to remove oxygen for 30 minutes, and then adding 0.02g of initiator KPS. The rotational speed of the mechanical stirring during the reaction was 300 r/min. Carrying out polymerization reaction for 4 hours; then add into10g of dibutyl itaconate and 16g of monomer n-butyl acrylate for adjusting the glass transition temperature, and 0.02g of initiator are added for polymerization reaction for 5 hours; then adding 10g of dibutyl itaconate and 0.5g of crosslinking point monomer glycidyl methacrylate, adding 0.02g of initiator, carrying out polymerization reaction for 4 hours, then adding 5g of dibutyl itaconate and 16g of monomer n-butyl acrylate for adjusting the glass transition temperature, adding 0.02g of initiator, and carrying out polymerization reaction for 5 hours; then 10g of dibutyl itaconate and 0.5g of crosslinking point monomer glycidyl methacrylate are added, 0.02g of initiator is added for polymerization reaction for 4 hours, 5g of dibutyl itaconate and 16g of monomer n-butyl acrylate for adjusting the glass transition temperature are added, 0.02g of initiator is added for polymerization reaction for 5 hours, cooling and discharging are carried out, 1% calcium chloride aqueous solution is adopted for flocculation, and drying is carried out.
TABLE 1 molecular weights and molecular weight distributions of polymers of different sequence structures in the examples
Claims (8)
1. The preparation method of the itaconate bio-based elastomer with the controllable sequence structure and the adjustable cross-linking point distribution is characterized in that itaconate monomers, glass transition temperature adjusting monomers and cross-linking point monomers are fed in sequence according to the required sequence structure sequence and the cross-linking point distribution, reversible addition-fragmentation chain transfer polymerization (RAFT) is adopted, and the emulsifier is polymerized by a soap-free emulsion polymerization method of forming micelles by using an amphiphilic RAFT reagent.
2. The preparation method of the itaconate bio-based elastomer with the controllable sequence structure and the adjustable cross-linking point distribution according to claim 1, is characterized by comprising the following steps:
closing the polymerization device, vacuumizing, and then filling argon to remove oxygen; adding deionized water, an RAFT reagent and a monomer into a reaction device, stirring and pre-emulsifying for 30-60min, preferably at a pre-emulsifying speed of 100-500 r/min, adding an initiator, reducing the rotating speed to 100-300 r/min, and heating to 40-80 ℃ for reaction; the total reaction time is 10-96 h; adding the RAFT reagent once, and adding the monomers and the initiator in batches for multiple times according to the required sequence structure and the distribution of cross-linking points;
the controllable sequence structure and the adjustable cross-linking point distribution mean that the corresponding sequence structure, the itaconate monomer corresponding to the cross-linking point, the monomer for adjusting the glass transition temperature and the cross-linking point monomer are added step by step or in batches for multiple times according to the required sequence structure and the cross-linking point distribution. If the sequence structure of the elastomer sequentially comprises an A block, a B block and a C block, wherein the cross-linking points are distributed on the corresponding A block or/and the B block or/and the C block, the addition sequence of the corresponding monomers is that an itaconate monomer corresponding to the A block, a monomer for adjusting the glass-transition temperature and a cross-linking point monomer are added for reaction, then an itaconate monomer corresponding to the B block, a monomer for adjusting the glass-transition temperature and a cross-linking point monomer are added for reaction, and an itaconate monomer corresponding to the C block, a monomer for adjusting the glass-transition temperature and a cross-linking point monomer are added for reaction. Wherein, the A block, the B block and the C block are polymerized blocks of one or more monomers of itaconate monomers, glass transition temperature adjusting monomers and crosslinking point monomers, and the A block, the B block and the C block can be the same or different; or adjusted as necessary, and different blocks may be added.
3. The preparation method of the itaconate bio-based elastomer with the controllable sequence structure and the adjustable cross-linking point distribution according to claim 2, wherein the total proportion of the monomers, the RAFT agent, the initiator and the deionized water is as follows: 100 parts of monomer, 0.5-10 parts of RAFT reagent, 0.005-0.05 part of initiator and 300 parts of deionized water.
4. The preparation method of itaconate bio-based elastomer with controllable sequence structure and adjustable cross-linking point distribution according to claim 2,
(A) the molecular formula of the itaconate ester monomer is as follows:
wherein R is1、R2Is a hydrogen atom or C1-12Alkyl of R1、R2The same or different; the weight portion of the itaconate is 50-99 parts, preferably 50-80 parts.
(B) Glass transition temperature adjusting monomers, wherein homopolymers of the monomers have lower glass transition temperature, and the monomers comprise n-propyl acrylate, n-butyl acrylate, 2-ethyl ethylhexyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and alkoxyether acrylate; the glass transition temperature adjusting monomer is 0-49 parts by weight, preferably 30-49 parts by weight;
(C) the crosslinking point monomer is a vinyl monomer with crosslinkable functional groups, such as amino, carboxyl, halogen, epoxy and the like, and can be one or more; the weight portion of the crosslinking point monomer is 1-10 weight portions, preferably 2-6 weight portions.
5. The method for preparing itaconate bio-based elastomer with controllable sequence structure and adjustable cross-linking point distribution according to claim 4, wherein the cross-linking point monomer is vinyl chloride-containing monomer selected from: chloroethyl vinyl ether, chloroethyl acrylate, vinylbenzyl chloride, vinyl chloroacetate, allyl chloroacetate, chloromethyl styrene;
the crosslinking point monomer is a vinyl monomer containing an epoxy group and is selected from: glycidyl acrylate, glycidyl methacrylate, diglycidyl tricarboxylate, triglycidyl tricarboxylate, propenyl glycidyl ether, methacryl glycidyl ether;
the crosslinking point monomer is a carboxyl-containing vinyl monomer selected from: acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic acid monoester;
the crosslinking point monomer is an amino-containing vinyl monomer selected from: acrylamide, dimethylaminoethyl methacrylate.
6. The method for preparing itaconate bio-based elastomer with controllable sequence structure and adjustable cross-linking point distribution according to claim 2, wherein the initiator is azobisisobutyronitrile, azobisisoheptonitrile, 4, 4' -azo (4-dicyano valeric acid), azobisisobutyrimidazoline hydrochloride, azobisisopropylimidazoline, dibenzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide or di-t-butyl peroxide; the initiator can be added in one portion or in each case in the corresponding block reaction, as desired.
7. The preparation method of the itaconate bio-based elastomer with the controllable sequence structure and the adjustable cross-linking point distribution according to claim 2, wherein the chemical structure general formula of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent is as follows:
AA is selected from acrylic acid units and methacrylic acid units, St is styrene units, R' is alkyl with carbon number from four to twelve, R is isopropyl acid group, acetic acid group, 2-cyanoacetic acid group, 2-amino acetic acid group and 2-methyl propionic acid group, wherein m is average polymerization degree, n is average polymerization degree of acrylic acid units or/and methacrylic acid units, m is 3-7, and n is 20-60.
8. An itaconate bio-based elastomer with controllable sequence structure and adjustable distribution of cross-linking points, prepared by the method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111119787.XA CN113912794A (en) | 2021-09-23 | 2021-09-23 | Itaconate bio-based elastomer with controllable sequence structure and adjustable cross-linking point distribution and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111119787.XA CN113912794A (en) | 2021-09-23 | 2021-09-23 | Itaconate bio-based elastomer with controllable sequence structure and adjustable cross-linking point distribution and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113912794A true CN113912794A (en) | 2022-01-11 |
Family
ID=79236068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111119787.XA Pending CN113912794A (en) | 2021-09-23 | 2021-09-23 | Itaconate bio-based elastomer with controllable sequence structure and adjustable cross-linking point distribution and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113912794A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015040043A1 (en) * | 2013-09-19 | 2015-03-26 | Synthomer Deutschland Gmbh | Triblock copolymers by raft polymerization in miniemulsion |
| CN104725756A (en) * | 2014-09-06 | 2015-06-24 | 北京化工大学 | Itaconate/isoprene copolymer type biology base elastomer tread rubber and preparation method thereof |
| CN107418125A (en) * | 2017-07-06 | 2017-12-01 | 浙江大学 | A kind of method that multiphase polymer material is prepared using segmented copolymer latex |
| CN109320658A (en) * | 2018-07-17 | 2019-02-12 | 湖北大学 | A kind of itaconate biology base heat resistant oils elastomer and preparation method thereof |
-
2021
- 2021-09-23 CN CN202111119787.XA patent/CN113912794A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015040043A1 (en) * | 2013-09-19 | 2015-03-26 | Synthomer Deutschland Gmbh | Triblock copolymers by raft polymerization in miniemulsion |
| CN104725756A (en) * | 2014-09-06 | 2015-06-24 | 北京化工大学 | Itaconate/isoprene copolymer type biology base elastomer tread rubber and preparation method thereof |
| CN107418125A (en) * | 2017-07-06 | 2017-12-01 | 浙江大学 | A kind of method that multiphase polymer material is prepared using segmented copolymer latex |
| CN109320658A (en) * | 2018-07-17 | 2019-02-12 | 湖北大学 | A kind of itaconate biology base heat resistant oils elastomer and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| KOTARO SATOH等: "Precision Synthesis of Bio-Based Acrylic Thermoplastic Elastomer by RAFT Polymerization of Itaconic Acid Derivatives", vol. 35, pages 161 - 167 * |
| RENZHONG WEI等: "Ab Initio RAFT Emulsion Polymerization of Butadiene Using the Amphiphilic Poly(acrylic acid-b-styrene) Trithiocarbonate as Both Surfactant and Mediator RENZHONG", vol. 49, pages 2980 - 2989 * |
| 方亮: "《药用高分子材料学》", 国医药科技出版社, pages: 45 - 46 * |
| 王晓光: "RAFT乳液聚合机理及聚（苯乙烯-b-丙烯酸丁酯-b-苯乙烯）的制备", no. 05, pages 016 - 109 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ning et al. | Preparation, microstructure, and microstructure-properties relationship of thermoplastic vulcanizates (TPVs): A review | |
| US6100334A (en) | Thermoplastic vulcanizates from a cyclic olefin rubber, a polyolefin, and a compatiblizer | |
| JPH09137007A (en) | Vulcanized thermoplastic rubber made from isobutyrene rubberand epdm or conjugated diene rubber | |
| CN103228681B (en) | Phosphonium ion cross-linked polymer comprising pendant vinyl base and preparation method thereof | |
| JPH10195253A (en) | Preferable structure of phenol resin curing agent for thermoplastic vulcanizable rubber | |
| CN110452467A (en) | A kind of thermoplastic elastomer (TPE) and preparation method thereof with inierpeneirating network structure | |
| JP3998159B2 (en) | Method for producing a gel-free ethylene / vinyl acetate copolymer having a high content of copolymerized vinyl acetate and a high Mooney viscosity | |
| JP3599061B2 (en) | Thermoplastic elastomer based on polyolefin-polyacrylate | |
| CN108395505B (en) | Medium-impact polystyrene resin and preparation method thereof | |
| US20080058470A1 (en) | New polymers for bitumen modification & other uses | |
| Sun et al. | In situ reactive compatibilization of polypropylene/trans-1, 4-poly (isoprene-co-butadiene) rubber (TBIR) blends with balanced toughness and stiffness via dynamic vulcanization | |
| CN1317324C (en) | Production of thermoplastic elastomer | |
| JP3395617B2 (en) | Method for producing (meth) acrylic polymer blend composition | |
| CN113912794A (en) | Itaconate bio-based elastomer with controllable sequence structure and adjustable cross-linking point distribution and preparation method thereof | |
| CN109486060B (en) | PVC (polyvinyl chloride) extruded pipe for communication and preparation method thereof | |
| WO2010099645A1 (en) | Method for coupling polyolefin chains | |
| US4433107A (en) | Polyisoprene rubber compositions | |
| CN106928390B (en) | Method for preparing isobutylene and alkylstyrene polymer | |
| CN113498419B (en) | Acrylic copolymer coagulant and method for preparing graft copolymer using the same | |
| CN117062866A (en) | Self-healing rubber comprising poly (methacrylic acid) oligomers | |
| JP3985547B2 (en) | Thermoplastic elastomer composition and molded article | |
| CN1590445A (en) | Butyl rubber compositions comprising nitrile polymers | |
| JP4554836B2 (en) | Rubber composition | |
| JP4078862B2 (en) | Olefinic thermoplastic elastomer and molded article thereof | |
| CN1690110A (en) | Peroxide curable butyl formulations |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |