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KR-102802141-B9 - A RIGNIN MODIFIED PHENOLIC RESIN, PROCESS OF PREPARING THE RIGNIN MODIFIED PHENOLIC RESIN AND ARTICLE INCLUDING THE SAME

KR102802141B9KR 102802141 B9KR102802141 B9KR 102802141B9KR-102802141-B9

Abstract

The present invention relates to a lignin-modified phenolic resin, a method for manufacturing a lignin-modified phenolic resin, and a molded article comprising the same. The lignin-modified phenolic resin can be more suitablely used in molded articles requiring improved heat resistance and strength.

Inventors

  • 유정은
  • 김유성
  • 최평희
  • 장성봉

Assignees

  • 코오롱인더스트리 주식회사

Dates

Publication Date
20260513
Application Date
20220330
Priority Date
20210608

Claims (20)

  1. Repeating unit (a) derived from phenolic compounds; Repeating unit (b) derived from aldehyde compounds; and It includes repeating units (c) derived from lignin compounds, The weight of sulfur (S) contained in the above lignin compound is 1.0 to 3.0 parts by weight or less based on 100 parts by weight of the above lignin compound, and The number average molecular weight (Mn) of the above lignin compounds is 2,200 to 15,000 g/mol, the weight average molecular weight (Mw) is 5,000 to 33,000 g/mol, and the polymer density index (PDI) is 1 to 6. The weight average molecular weight (Mw) of the above lignin-modified phenolic resin is 900 to 1,500 g/mol, and The number average molecular weight (Mn) of the above lignin-modified phenolic resin is 300 g/mol to 500 g/mol, and The above lignin-modified phenolic resin is a resol resin, a lignin-modified phenolic resin.
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  4. In paragraph 1, The above-mentioned lignin compound is a lignin-modified phenolic resin comprising Kraft lignin, alkali lignin, or a combination thereof.
  5. In paragraph 1, The above phenolic compound is a lignin-modified phenolic resin, which is a compound represented by the following chemical formula 1: <Chemical Formula 1> Among the above chemical formula 1, R1 is hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, a substituted or unsubstituted C1 - C60 alkyl group substituted or unsubstituted with at least one R10a , a substituted or unsubstituted C2 - C60 alkenyl group substituted or unsubstituted with at least one R10a , a substituted or unsubstituted C2 - C60 alkynyl group substituted or unsubstituted with at least one R10a , a substituted or unsubstituted C1 - C60 alkoxy group substituted or unsubstituted with at least one R10a , a C3 - C60 carbocyclic group substituted or unsubstituted with at least one R10a , a C1 - C60 heterocyclic group substituted or unsubstituted with at least one R10a , a C6 - C60 group substituted or unsubstituted with at least one R10a An aryloxy group, a C6 - C60 aryltio group substituted or unsubstituted with at least one R10a , a C7 - C60 arylalkyl group substituted or unsubstituted with at least one R10a , a C2 - C60 heteroarylalkyl group substituted or unsubstituted with at least one R10a , -Si( Q1 )(Q2)( Q3 ), -N( Q1 )( Q2 ), -B( Q1 )( Q2 ), -C(=O) (Q1 ) , -S(=O) 2 ( Q1 ) or -P(=O)( Q1 )( Q2 ), and The above R 10a is, Deuterium (-D), -F, -Cl, -Br, -I, hydroxyl group, cyano group, or nitro group; Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, C3 - C60 carbocyclic group, C1 - C60 heterocyclic group, C6 - C60 aryloxy group, C6 - C60 arylthio group, C7 - C60 arylalkyl group, C2 - C60 heteroarylalkyl group, -Si( Q11 )( Q12 )( Q13 ), -N( Q11 )( Q12 ), -B( Q11)(Q12 ) , -C(=O)( Q11 ), -S(=O) 2 ( Q11 ), -P(=O)( Q11 )( Q12 ), or any combination thereof, C1 - C60 alkyl group, C2 -C60 alkenyl group, C2 - C60 alkynyl group, or C1 - C60 alkoxy group; Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, C1 - C60 alkyl group, C2 - C60 alkenyl group, C2 - C60 alkynyl group, C1 - C60 alkoxy group, C3 - C60 carbocyclic group, C1 - C60 heterocyclic group, C6 - C60 aryloxy group, C6 - C60 arylthio group, C7 - C60 arylalkyl group, C2 - C60 heteroarylalkyl group, -Si( Q21 )( Q22 )( Q23 ), -N( Q21 )( Q22 ), -B( Q21)(Q22 ) , -C(=O)( Q21 ), -S(=O) 2 (Q 21 ), -P(=O)(Q 21 )(Q 22 ), or any combination thereof, substituted or unsubstituted with a C 3 -C 60 carbocyclic group, a C 1 -C 60 heterocyclic group, a C 6 -C 60 aryloxy group, a C 6 -C 60 arylthio group, a C 7 -C 60 arylalkyl group, or a C 2 -C 60 heteroarylalkyl group; or -Si(Q 31 )(Q 32 )(Q 33 ), -N(Q 31 )(Q 32 ), -B(Q 31 )(Q 32 ), -C(=O)(Q 31 ), -S(=O) 2 (Q 31 ), or -P(=O)(Q 31 )(Q 32 ); And, The above Q1 to Q3 , Q11 to Q13 , Q21 to Q23 , and Q31 to Q33 are independently hydrogen; deuterium; -F; -Cl; -Br; -I; hydroxyl group; cyano group; nitro group; C1 - C60 alkyl group; C2 - C60 alkenyl group; C2 - C60 alkynyl group; C1- C60 alkoxy group; or a C3 -C60 carbocyclic group, C1 - C60 heterocyclic group; C7 - C60 arylalkyl group, substituted or unsubstituted with deuterium, -F, cyano group, C1 - C60 alkyl group, C1 - C60 alkoxy group, phenyl group, biphenyl group, or any combination thereof; or a C2 - C60 heteroarylalkyl group; and, a1 is an integer from 0 to 5.
  6. In paragraph 1, The above aldehyde compound is a lignin-modified phenol resin, which is a compound represented by the following chemical formula 2: <Chemical Formula 2> Among the above chemical formula 2, R2 is hydrogen, deuterium, C1 - C60 alkyl group, C2 - C60 alkenyl group, C2 - C60 alkynyl group, C1 - C60 alkoxy group, -C(=O)( Q11 ); or Deuterium, a C1 - C60 alkyl group, a C2 - C60 alkenyl group, a C2 - C60 alkynyl group, a C1 - C60 alkoxy group, a C3 - C60 carbocyclic group, a C1 - C60 heterocyclic group, or a C6 - C60 aryloxy group substituted or unsubstituted with -C(=O)( Q1 ) or any combination thereof; and Q1 is hydrogen; deuterium; -F; -Cl; -Br; -I; hydroxyl group; cyano group; nitro group; C1 - C60 alkyl group; C2 - C60 alkenyl group; C2 - C60 alkynyl group; C1 - C60 alkoxy group; or a C3-C60 carbocyclic group, C1 - C60 heterocyclic group; C7 - C60 arylalkyl group; or C2 - C60 heteroarylalkyl group, substituted or unsubstituted with deuterium, -F, cyano group, C1 - C60 alkyl group, C1 - C60 alkoxy group, phenyl group, biphenyl group, or any combination thereof.
  7. In paragraph 1, A lignin-modified phenolic resin in which the molar ratio (mol%) of repeating units (c) derived from the lignin compound in the lignin-modified phenolic resin is 0.5 to 20 mol% relative to the total molar amount of repeating units contained in the lignin-modified phenolic resin.
  8. In paragraph 1, A lignin-modified phenolic resin in which the ratio of the total number of moles of repeating units (b) derived from the aldehyde compound to the total number of moles of repeating units (a) derived from the phenol compound in the lignin-modified phenolic resin is 1 to 3.
  9. In paragraph 1, A lignin-modified phenolic resin in which the molar ratio (mol%) of the repeating unit (a) derived from the phenolic compound in the lignin-modified phenolic resin is 20 to 70 mol% with respect to the total number of repeating units contained in the lignin-modified phenolic resin.
  10. In paragraph 1, A lignin-modified phenolic resin having a residual carbon content of 20% to 50%.
  11. In paragraph 1, The above lignin-modified phenolic resin has a PDI of 2 to 5, and is a lignin-modified phenolic resin.
  12. In paragraph 1, A lignin-modified phenolic resin having a viscosity of 400 cps to 3,000 cps at 25°C.
  13. (a) a step of obtaining a phenol resin composition by reacting a phenol compound, an aldehyde compound and a lignin compound in the presence of a basic catalyst; comprising, The weight of sulfur (S) contained in the above lignin compound is 1.0 to 3.0 parts by weight or less based on 100 parts by weight of the above lignin compound, and A method for preparing a lignin-modified phenolic resin, wherein the number average molecular weight (Mn) of the above-mentioned lignin compound is 2,200 to 15,000 g/mol, the weight average molecular weight (Mw) is 5,000 to 33,000 g/mol, and the polymer density index (PDI) is 1 to 6, The weight average molecular weight (Mw) of the above lignin-modified phenolic resin is 900 to 1,500 g/mol, and The number average molecular weight (Mn) of the above lignin-modified phenolic resin is 300 g/mol to 500 g/mol, and A method for manufacturing a lignin-modified phenolic resin, wherein the above lignin-modified phenolic resin is a resol resin.
  14. In Paragraph 13, A method for preparing a lignin-modified phenolic resin, wherein in step (a) of obtaining the above phenolic resin composition, the ratio of the molar amount of the aldehyde compound to the molar amount of the phenolic compound is 1 to 3.
  15. In Paragraph 13, A method for producing a lignin-modified phenolic resin, wherein in step (a) of obtaining the phenolic resin composition, the weight ratio (weight%) of the phenolic compound is 20 to 70 weight% with respect to the total sum of the weight of the phenolic compound, the weight of the aldehyde compound, and the weight of the lignin compound included in the phenolic resin composition.
  16. In Paragraph 13, A method for producing a lignin-modified phenolic resin, wherein in step (a) of obtaining the phenolic resin, the weight ratio (weight%) of the catalyst to the weight of the phenolic compound is 0.5 to 5 weight%.
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  18. In Paragraph 13, (b) a step of adding a thickening agent and a neutralizing agent to the phenol resin composition; further comprising a method for manufacturing a lignin-modified phenol resin.
  19. In Paragraph 18, A method for manufacturing a lignin-modified phenolic resin, wherein the above-mentioned thickener comprises a glycol-based thickener and the above-mentioned neutralizing agent comprises a carboxylic acid-based neutralizing agent.
  20. A molded body comprising a lignin-modified phenolic resin according to any one of claims 1 and 4 to 12.

Description

A RIGNIN MODIFIED PHENOLIC RESIN, PROCESS OF PREPARING THE RIGNIN MODIFIED PHENOLIC RESIN AND ARTICLE INCLUDING THE SAME The present invention relates to a lignin-modified phenolic resin, a method for manufacturing a lignin-modified phenolic resin, and a molded article comprising the same. Woody waste (biomass), such as tree bark, thinning wood, and construction waste, has been disposed of until now. However, as environmental pollution issues have recently become a major challenge, methods for the reuse and recycling of the aforementioned biomass have begun to be considered. The main components of the above biomass include cellulose, hemicellulose, and lignin. Among these, lignin, which is included in a ratio of about 30% by weight, has a structure rich in aromatic rings, phenolic hydroxyl groups, and alcoholic hydroxyl groups, so its use as a raw material for resin is being considered. In this regard, chemical products such as resins have traditionally used fossil resources, such as petroleum, as raw materials. However, with the recent introduction of the concept of carbon neutrality, there has been a growing demand to use the aforementioned biomass as a raw material. Consequently, there has been active movement to incorporate plant-derived resins (bioplastics) into plastic products, such as packaging materials, components for home appliances, and automotive parts. In particular, biomass (e.g., trees) forms an interpenetrating polymer network (IPN) structure of hydrophilic linear polymeric polysaccharides (cellulose and hemicellulose) and hydrophobic cross-linked lignin. Among the above biomass, lignin has been attracting attention as a raw material for plant-derived heat-resistant resins. Lignin is a cross-linked polymer with a basic framework of hydroxyphenylpropane units and has the chemical structure of polyphenols, which account for about 25 mass% of biomass. Accordingly, lignin is attracting attention as a substitute raw material for petroleum-derived phenolic resins. However, resins manufactured using raw materials of general plant-derived heat-resistant resins faced the problem of being unable to simultaneously satisfy sufficient heat resistance, processability, and strength. In particular, although lignin is expected to have superior heat resistance compared to other bioplastics such as polylactic acid, it possesses alcoholic and phenolic hydroxyl groups, resulting in higher softening temperatures and melting points compared to general phenolic resins, which led to a problem of reduced processability. Consequently, there were limitations in its application to automotive parts, OA-related parts, molded bodies, and cast products. Hereinafter, various aspects and various embodiments of the present invention will be described in more detail. Terms and words used in this specification and claims shall not be interpreted as being limited to their ordinary or dictionary meanings, but shall be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention. The terms used in this invention are used merely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this invention, terms such as "comprising" or "having" are intended to indicate the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof. Specifically, one aspect of the present invention provides a lignin-modified phenolic resin comprising a repeating unit (a) derived from a phenolic compound; a repeating unit (b) derived from an aldehyde compound; and a repeating unit (c) derived from a lignin compound, wherein the weight of sulfur (S) contained in the lignin compound is 3.0 parts by weight or less based on 100 parts by weight of the lignin compound. For example, the above lignin compounds may refer to high-molecular-weight phenolic compounds composed of basic frameworks such as gyacirrh lignin (G type), syringyr lignin (S type), and p-hydroxyphenyl lignin (H type). The above-mentioned lignin compounds are compounds found throughout plants and may refer to compounds derived from any one of the woods of broadleaf, coniferous, and herbaceous trees. For example, lignin derived from wood of the broadleaf tree series may include G-type lignin and S-type lignin. For example, lignin derived from wood of the coniferous tree series may include G-type lignin. For example, lignin derived from wood of the herbaceous tree series may include H-type, G-type, and S-type. The above lignin compounds may be extracted from natural lignin contained in wood. For exa