WO2019112203A1 - Nouveau composé d'agent de réticulation et polymère préparé à l'aide de celui-ci - Google Patents

Nouveau composé d'agent de réticulation et polymère préparé à l'aide de celui-ci Download PDF

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Publication number
WO2019112203A1
WO2019112203A1 PCT/KR2018/014281 KR2018014281W WO2019112203A1 WO 2019112203 A1 WO2019112203 A1 WO 2019112203A1 KR 2018014281 W KR2018014281 W KR 2018014281W WO 2019112203 A1 WO2019112203 A1 WO 2019112203A1
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Prior art keywords
carbon atoms
formula
compound
methyl
linear
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PCT/KR2018/014281
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English (en)
Korean (ko)
Inventor
임원택
최원문
김기철
김기현
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주식회사 엘지화학
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Priority claimed from KR1020180139993A external-priority patent/KR102364365B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/770,887 priority Critical patent/US11560463B2/en
Priority to EP18885147.1A priority patent/EP3702402B1/fr
Priority to CN201880078028.3A priority patent/CN111433267B/zh
Priority to JP2020516441A priority patent/JP6980908B2/ja
Publication of WO2019112203A1 publication Critical patent/WO2019112203A1/fr

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    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids

Definitions

  • the present invention relates to a novel crosslinking compound and a polymer prepared using the same. More particularly, the present invention relates to a crosslinking compound having a novel structure exhibiting excellent crosslinking properties and thermal decomposability, and a polymer produced using the same.
  • Super Absorbent Polymer is a synthetic polymer material capable of absorbing moisture from about 500 to 1,000 times the weight of lanzai. It is a synthetic polymer material with a super absorbent material (SAM), an absorbent gel material ), And so on.
  • SAM super absorbent material
  • Such a superabsorbent resin has started to be put into practical use as a sanitary article and is currently being used for sanitary articles such as diapers for children and sanitary napkins as well as soil repair agents for horticultural use, index materials for construction and construction, seedling- , And as a material for fomentation and the like.
  • the base resin which is an important constituent polymer, should have high absorption capacity.
  • the internal cross-linking agent is a polymer obtained by polymerizing an acrylic acid-based monomer
  • the internal crosslinking density of the base resin can be adjusted according to the type and content of the internal crosslinking agent.
  • the cross-linking density of the base resin is low, the absorption capacity is increased, but the strength is weak, so that the shape can not be maintained in a subsequent step.
  • the cross-linking density is too high, the strength becomes high, It is very important to control the proper crosslinking density from the viewpoint of absorption ability and absorption ability.
  • the aqueous acrylic resin prepared by polymerizing an acrylic acid monomer has a characteristic odor of acrylic acid, and when it is used in sanitary articles such as diapers, it is accompanied by an unpleasant smell when urine or the like is excreted, thereby effectively reducing the odor rate Is required.
  • a method of using a porous adsorbent material in combination with a superabsorbent resin has been developed.
  • the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a crosslinking compound having a novel structure which can be used as a crosslinking agent in the production of an aqueous resin, and which is excellent in crosslinking properties, thermal decomposability and odor characteristics, I want to.
  • Each of phlogop and ⁇ is independently hydrogen or methyl
  • Each of 3 ⁇ 4 and 3 ⁇ 4 is independently hydrogen or alkyl (s) having 1 to 20 carbon atoms,
  • a polymer obtained by polymerizing the crosslinking compound and an acrylic acid-based monomer obtained by polymerizing the crosslinking compound and an acrylic acid-based monomer.
  • the polymer prepared by using the crosslinking compound of the present invention exhibits a high crosslinking density immediately after polymerization and has high strength and excellent processability.
  • the internal crosslinking structure is decomposed and the crosslinking density is lowered, .
  • the crosslinking compound of the present invention exhibits a deodorizing ability to reduce the odor generated when it is used as an odor and / or a sanitary article peculiar to a superabsorbent resin without a special additive due to its unique fragrance, You can provide feeling. 2019/112203 1 »(: 1 ⁇ 1 ⁇ 2018/014281
  • crosslinking compound of the present invention and the polymer produced using the crosslinking compound will be described in more detail.
  • crosslinking compound according to one embodiment of the present invention is represented by the following formula (1).
  • R < 3 > and R < 4 &gt is independently hydrogen or alkyl of 1 to 20 carbon atoms
  • alkyl &quot means a linear or branched, saturated monovalent hydrocarbon of 1 to 20, preferably 1 to 10, more preferably 1 to 5 carbon atoms.
  • alkyl include methyl, ethyl, propyl, 11-propyl, isopropyl, 2019/112203 1 »(: 1 ⁇ 1 ⁇ 2018/014281
  • a linear or branched, saturated divalent hydrocarbon of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
  • alkylenes include methylene, ethylene, propyleneglycol, Butylene, nuclear silicone, heptyl, octylene and the like, but the present invention is not limited thereto.
  • alkenyl (-1) &quot refers to a linear or branched (linear or branched) alkyl group having from 2 to 20, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms, Alkenyl may be bonded through a carbon atom containing a carbon-carbon double bond and / or through a saturated carbon atom.
  • alkenyl include allyl, 1-propenyl, 1-propenyl, Isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl,
  • alkenylene halide phrase refers to a linear or branched, branched or cyclic, branched or unbranched alkyl group having from 2 to 20, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms, Refers to a bivalent hydrocarbon of the general formula I.
  • Alkenylenes may be bonded through a carbon atom containing a carbon-carbon double bond and / or through a saturated carbon atom. Examples of alkenylene include ethenylene, propenylene, butenylene And the like, but the present invention is not limited thereto.
  • the crosslinking compound of Formula 1 has a novel structure as a di (meth) acrylate derivative compound.
  • the nitrogen and the sulfur may be hydrogen.
  • the above-mentioned and the following may be alkyl having 1 to 5 carbon atoms.
  • the above-mentioned and the following may be methyl. 2019/112203 1 »(: 1 ⁇ 1 ⁇ 2018/014281
  • the above-mentioned group is a linear or branched alkylene having 1 to 10 carbon atoms substituted with an alkenyl having 1 to 10 carbon atoms, or a linear or branched alkenylene having 2 to 10 carbon atoms .
  • the 1, 3-methyl-2-Nuclear xylene (3-111 1171-2-116 table 4611 ⁇ , 3-methyl-1-nuclear xylene (3- 1 ⁇ 1>, 1-1 ⁇ 6 ⁇ , 611 ⁇ 1, 4, 8-dimethyl-undeca-3, 7-diethoxy alkenylene (4,8- (iimethylimdeca-3,7- dienyl e n e) , but be the like, the present invention is not limited thereto no.
  • II may be an integer of 0 to 10.
  • II may be an integer of 0 to 5, or 0 to 3.
  • the compound represented by Formula 1 may be any one selected from the group consisting of Formulas 1-1 through 1-3, but the present invention is not limited thereto.
  • the use of the compound represented by the formula (1) is not limited thereto, but may be used as a crosslinking agent in polymerization with an acrylic acid-based monomer.
  • the crosslinking compound of formula (1) can be prepared by a known organic synthesis method, for example, by the following reaction scheme 1, but the present invention is not limited thereto.
  • the present invention when the compound of formula (I) is a compound of formula (1-1) or (1-2), the present invention is not limited thereto.
  • the myrcene and geraniol are derivative compounds of the terpene group.
  • Terpenes are flammable, unsaturated hydrocarbons widely distributed in flora and fauna and are classified according to the number of isoprene (3 ⁇ 4) units in the molecule, and monoterpene ((: 1 one is 3: (151 3 ⁇ 4 4 () , di-terpenes ([: 2 (): 3 ⁇ 4 2) () 11 16) is two, sesqui terpenes may have each four isoprene units.
  • Monterpenes, sesquiterpenes, and diterpenes are found in plant essential oils (position 1), and are used as raw materials for spices, raw materials for pharmaceuticals and the chemical industry.
  • terpenes, terpene alcohols, terpene aldehydes, terpene ketones, terpene oxides , terpene lactones and the like are collectively referred to as terpenoids.
  • Mirensen (1115 11) is a kind of mono terpene, found in abundance in essential oils in a large number of plants, including hops, lemon grass, thyme, verbena, and bay leaves, and has a unique herbal flavor.
  • Geraniolum is a kind of monoterpenoid, which is also included in various essential oils such as geranium and lemon. It is not soluble in water, but is easily soluble in most common organic solvents and has an aroma like a rose. 2019/112203 1 »(: 1/10/0/0 018/014281
  • the polymer is crosslinked using a natural terpene such as myrcene or geraniol as a starting material and a compound of the formula (1) is used as a crosslinking agent
  • a compound of the formula (1) when the crosslinking agent is decomposed at a high temperature, the original myrcene or geraniol So that a deodorizing effect can be obtained and a perfume can be expressed even without a separate additive.
  • the cross-linking compound of Formula 1-1 and 1-2 may be prepared by the following Reaction Schemes 2-1 and 3.
  • the temperature is cooled to room temperature. Thereafter, the solid precipitate is removed by using a filter filter, and the remaining acetone is removed by evaporation under reduced pressure. The remaining organic matter and a small amount of water A mixture with the desired diol compound can be obtained.)
  • the diol compound is prepared according to Reaction Scheme 2-1, the compound Compound Can be confirmed.
  • An acryloyl group can be introduced into the mixture by the following reaction formula (3).
  • the compounds of the formulas (1-1) and (1-2) obtained above may be used as separated or purified, or may be used in the form of a mixture without isolation.
  • the crosslinking compound of the formula (1-1) and (1-2) can be prepared by the following reaction formulas 2-2 and 3.
  • the solid precipitate is removed by using a filter filter, and the remaining acetic acid is removed by evaporation under reduced pressure.
  • Methanol is added to the remaining organic material, and about 2 equivalents of potassium carbonate (K 2 CO 3) is added, and the mixture is refluxed and stirred.
  • TLC is used to check the conversion of the reaction.
  • the reaction temperature is cooled to room temperature.
  • the methanol is removed by evaporation under reduced pressure, and the remaining organic material is distilled under reduced pressure to obtain a diol compound (mixture of Pa and Ta).
  • Reaction Scheme 2-2 it can be confirmed that the amount of compound Pa is increased compared with that of compound Ta, and substantially only compound Pa is detected (Pa compound: molar ratio of Ta compound is 25: 1 or more) .
  • an acryloyl group can be introduced into the above mixture of Pa and Ta by the above-mentioned Reaction Scheme 3.
  • the compounds of the above-mentioned formulas (1-1) and (1-2) can be used separately, purified or used in the form of a mixture without separation.
  • a polymer obtained by cross-linking a cross-linking compound represented by the general formula (1) and an acrylic acid-based monomer there is provided a polymer obtained by cross-linking a cross-linking compound represented by the general formula (1) and an acrylic acid-based monomer.
  • the acrylic acid-based monomer is a compound represented by the following formula (2)
  • M is a hydrogen atom, a monovalent or divalent metal, an ammonium group or an organic amine salt.
  • the acrylic acid-based monomer includes at least one selected from the group consisting of acrylic acid, methacrylic acid, monovalent metal salts thereof, bivalent metal salts, ammonium salts and organic amine salts thereof.
  • the acrylic acid-based monomer may have an acidic group and at least a part of the acidic groups may be neutralized.
  • polymer or “cross-linked polymer” means that the acrylic acid-based monomer is polymerized in the presence of the cross-linking compound of the above formula (1), and includes all the moisture content ranges or particle diameter ranges Among the above polymers, a polymer having a water content (moisture content) of about 40% by weight or more after polymerization and before drying can be referred to as a hydrogel polymer.
  • base resin or “base resin powder " 'suspending polymer is dried and pulverized to obtain powder ( ! , ( ⁇ 1) means a polymer in which the crosslinking structure is not formed on the surface of the polymer before the surface cross-linking step is carried out.
  • the cross-linking compound represented by the formula ( 1 ) is a thermally decomposable internal cross-linking agent, and the internal cross-linking structure of the cross-linked polymer of the compound of the formula (1) and the acrylic acid-based monomer can be decomposed by heat (for example, at 150 degrees or more). Accordingly, when the acrylic acid-based monomer is crosslinked and polymerized in the presence of the crosslinking compound of Formula 1, a crosslinked polymer having a pyrolytic internal crosslinking structure introduced therein can be provided.
  • crosslinked polymer is introduced into a subsequent step at a high temperature such as a surface crosslinking step, the crosslinked structure derived from the compound of the formula (1) in the crosslinked polymer is at least partially decomposed. As a result, the internal crosslinking density in the crosslinked polymer is reduced. On the other hand, the surface of the crosslinked polymer is further crosslinked by the surface crosslinking agent to increase the external crosslinking density.
  • the base resin is prepared by proceeding the cross-linking polymerization of the acrylic acid monomer in the presence of the cross-linking compound represented by the above-mentioned formula (1) and the subsequent step such as surface cross-linking is performed on the base resin, the internal cross-linking structure in the cross- 2019/112203 1 »(: 1 ⁇ 1 ⁇ 2018/014281
  • the surface of the polymer is further cross-linked so that a superabsorbent resin in which the cross-link density increases from the inside to the outside of the resin can be obtained.
  • the superabsorbent resin thus produced may have a reduced internal crosslinking density than the base resin of the conventional superabsorbent resin. Accordingly, the superabsorbent resin can exhibit a relatively improved maintenance performance compared to the conventional superabsorbent resin.
  • the superabsorbent resin may have a thicker surface cross-linked layer than the conventional superabsorbent resin after the internal cross-linking is decomposed or the surface cross-linking proceeds while decomposing. Thus, the superabsorbent resin can exhibit excellent pressure-absorbing ability.
  • the superabsorbent resin of one embodiment increases in cross-link density from the inside to the outside and has a maintenance capacity and a pressure absorption capacity inversely proportional to each other, various physical properties such as water retention capacity and pressure absorption capacity It is possible to exhibit both excellent characteristics.
  • the polymer may be a cross-linking agent that is conventionally known.
  • a compound containing two or more crosslinkable functional groups in the molecule can be used.
  • the conventional internal crosslinking agents include N, N'-methylenebisacrylamide, trimethylol propane tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, propylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, polyoxyethylene (meth) acrylate, polypropylene glycol (meth) acrylate, butane diol di (Meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipentaerythritol pentaacrylate, glycerin tri Pentaerythritol tetraacrylate, triaryl acrylate Ethylene glycol digly
  • the polymer of the present invention is partially decomposed in a subsequent process at a high temperature after the polymerization process due to the characteristics of the novel crosslinking compound of the formula (1), and the crosslinking density is increased It is possible to exhibit very excellent properties in which various properties such as water retention ability and pressure absorption ability are improved together.
  • the crosslinking compound of the present invention since the crosslinking compound of the present invention has a unique scent due to the structural characteristics, it exhibits a deodorizing performance that reduces the odor generated upon use as a scent unique to a superabsorbent resin and / or a sanitary article without any additive, .
  • the superabsorbent resin can provide a sanitary article such as a diaper exhibiting excellent absorbent physical properties and odor characteristics even when subjected to a high-temperature production process.
  • Geraniol 408. was dissolved in ethanol 700 1111 and stirred. The reaction temperature was 301: while keeping the acetic chloride (La ⁇ 1 01 ⁇ ) (942 ⁇ 2019/112203 1 »(: 1 ⁇ 1 ⁇ 2018/014281
  • the mixture of the dichloronate compound (1) (522.9 g, the reference material) obtained in the above Synthesis Example 1-1 was purified with about 80% purity. (427.2 & 2.1 eq.) Was added thereto, and the mixture was refluxed at a temperature of 100 ° C. The reaction temperature was checked at room temperature by confirming the reaction (: 0 011) using 11 (:). Thereafter, the solid precipitate was removed using a filter filter, and the remaining acetone was removed by evaporation under reduced pressure. The remaining organic matter and a small amount of water are fractionated to obtain the desired diol compound Mixture).
  • the diol compound (51.7 and the reference material) obtained in the above Synthesis Example 1-2 was dissolved in 03 ⁇ 4 2 (3 ⁇ 4 (3001111) and the temperature was lowered with stirring while stirring.
  • Acryloyl chloride (57.0 & 51.01111, 2.1 equiv.) was slowly added after addition of triethylamine (91.1 & 125.41111, 3 equiv.) And 4- dimethylaminopyridine (7.3 & 0.1 equiv.). After the addition was completed, the reaction temperature was raised to room temperature and stirred for about 6 hours.
  • the dichlorocarbonate compound (313.7 g, reference material) obtained in Synthesis Example 1-1 was added to acetic acid (2 L), ZnO (256.3 g, 2.1 equivalent) was added thereto, and the mixture was stirred at room temperature . TLC was used to confirm the reaction and conversion. When the reaction was complete, the solid precipitate was removed by filtration and the remaining acetic acid was removed by evaporation under reduced pressure. Methanol (1 L) was added to the remaining organic matters, and K 2 CO 3 (470.0 g, 2 equivalents) was added thereto, followed by stirring under reflux. TLC was used to check the conversion of the reaction. When the reaction was complete, the reaction temperature was cooled to room temperature. Methanol was removed by evaporation under reduced pressure, and the remaining organic matters were distilled under reduced pressure to obtain a diol compound (Pa compound: Ta compound> substantially only a Pa compound was detected at a 25: 1 molar ratio).
  • the monomer composition was fed onto a rotating belt having a width of 10 cm and a length of 2 m and rotating at a speed of 50 cm / min at a feed rate of 500 mL / min to 2,000 tnL / min.
  • ultraviolet rays having an intensity of 10 inW / cm 2 were irradiated and the polymerization reaction was carried out for 60 seconds.
  • the polymerization reaction proceeded, it was cut with a meat chopper method and dried at 185 ° C for 40 minutes using an air-flow oven to prepare a superabsorbent resin (base resin).
  • base resin base resin
  • the aqueous resin was prepared in the same manner as in Example 1 except that the crosslinking compound 0 of Synthesis Example 2-2 was used.
  • Example 3
  • a superabsorbent resin was prepared in the same manner as in Example 1, except that 0.6 ⁇ of the crosslinking compound of Synthesis Example 3 was used.
  • Example 4
  • the aqueous resin was prepared in the same manner as in Example 1 except that the crosslinking compound 0.6 of Synthesis Example 4-2 was used. Comparative Example 1
  • a superabsorbent resin was prepared in the same manner as in Example 1, except that it was used.
  • the ability of the superabsorbent resin to absorb the physiological saline at zero load capacity was measured according to EDANA WSP 241.3. Specifically, a sample having a particle diameter of 150 to 850 / mm, which is passed through a US standard 20 mesh screen and is kept on a US standard 100 mesh screen, is prepared from the superabsorbent resin to be tested for centrifugal separation capability. 2019/112203 1 »(: 1 ⁇ 1 ⁇ 2018/014281
  • the particle size is uniformly into a 150 to 850 sample ssaenin 0 (about 0.2 & poe the envelope of the nonwoven fabric were sealed (86). Then, the envelope was immersed in an aqueous 0.9% by weight sodium chloride solution (physiological saline) at room temperature. After 30 minutes, the envelope was dehydrated for 3 minutes at 250 ° C using a centrifuge and the weight of the envelope was measured. On the other hand, after the same operation was performed using a blank envelope containing no sample, the weight at that time was measured.
  • ⁇ is the weight of the non-woven fabric empty bag measured after immersing the non-woven fabric empty bag without sample in physiological saline at room temperature for 30 minutes and then dehydrating at 250 for 3 minutes using a centrifuge
  • Comparative Example 1 using the conventional crosslinking agent did not show a significant increase in the walking ability after the heat treatment time.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un nouveau composé d'agent de réticulation et un polymère préparé à l'aide de celui-ci et, plus spécifiquement : un composé d'agent de réticulation ayant une nouvelle structure, présentant une excellente caractéristique de réticulation et une propriété de décomposition thermique; et un polymère préparé à l'aide de celui-ci.
PCT/KR2018/014281 2017-12-08 2018-11-20 Nouveau composé d'agent de réticulation et polymère préparé à l'aide de celui-ci WO2019112203A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/770,887 US11560463B2 (en) 2017-12-08 2018-11-20 Cross-linking agent compound and polymer prepared using the same
EP18885147.1A EP3702402B1 (fr) 2017-12-08 2018-11-20 Nouveau composé d'agent de réticulation et polymère préparé à l'aide de celui-ci
CN201880078028.3A CN111433267B (zh) 2017-12-08 2018-11-20 新的交联剂化合物和使用其制备的聚合物
JP2020516441A JP6980908B2 (ja) 2017-12-08 2018-11-20 新規な架橋剤化合物およびこれを用いて製造される重合体

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170168683 2017-12-08
KR10-2017-0168683 2017-12-08
KR10-2018-0139993 2018-11-14
KR1020180139993A KR102364365B1 (ko) 2017-12-08 2018-11-14 신규한 가교제 화합물 및 이를 이용하여 제조되는 중합체

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160117180A (ko) * 2015-03-30 2016-10-10 한화케미칼 주식회사 고 흡수성 수지의 제조방법
KR20180043143A (ko) * 2016-10-19 2018-04-27 주식회사 엘지화학 고흡수성 수지의 제조 방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160117180A (ko) * 2015-03-30 2016-10-10 한화케미칼 주식회사 고 흡수성 수지의 제조방법
KR20180043143A (ko) * 2016-10-19 2018-04-27 주식회사 엘지화학 고흡수성 수지의 제조 방법

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Title
GORODETSKAYA, I. A. ET AL.: "Functionalized Hyperbranched Polymers via Olefin Metathesis", MACROMOLECULES, vol. 42, no. 8, 28 April 2009 (2009-04-28), pages 2895 - 2898, XP055616591 *
KRITSKAYA, D. A. ET AL.: "A Model of the Formation of Branched Polymethyl-Methaciylates", RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B, vol. 3, no. 5, October 2009 (2009-10-01), pages 835 - 843, XP055616585 *
O'BRIEN, N. ET AL.: "Facile, Versatile and Cost Effective Route to Branched-vinyl Polymers", POLYMER, vol. 41, 2000, pages 6027 - 6031, XP004193920, doi:10.1016/S0032-3861(00)00016-1 *
See also references of EP3702402A4 *

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