WO2015185963A1

WO2015185963A1 - Procedure for obtaining plasticizer polymers and plasticizing polymers based on agents of plant origin for use in polymers

Info

Publication number: WO2015185963A1
Application number: PCT/IB2014/061991
Authority: WO
Inventors: Clovis PADOVANI; Anderson NICOLAI; Hugo WIZENBERG; Albio CALVETE ROTTA
Original assignee: Sion Nanotec
Priority date: 2014-06-05
Filing date: 2014-06-05
Publication date: 2015-12-10

Abstract

Primary plasticizers have a level of reactivity and compatibility with PVC due to the aromatic ring reacting with chlorinated groups and the decrease of intermolecular forces. The present invention introduces the concept of an epoxidized glycolic aryl triester with high reactivity, excess of free hydroxyl groups in compounds capable of increasing elongation, tear, traction, and as its base is vegetable fatty acid, increasing the thermal stability, which allows the compound an external and internal plasticizing effect with high resistance against thermal degradations. The present invention allows this plasticizer to be used in pvc articles in footwear, furniture, and stickers with no carcinogenic agent or agents that attack the environment.

Description

" ROCEDURE FOR OBTAINING PLASTICIZER POLYMERS AND PLASTICIZING POLYMERS BASED ON AGENTS OF PLANT ORIGIN FOR

USE IN POLYMERS"

ABSTRACT

[001] Primary plasticizers have a level of reactivity and compatibility with PVC due to the aromatic ring reacting with chlorinated groups and the decrease of intermolecular forces. The present invention introduces the concept of an epoxidized glycolic aryl triester with high reactivity, excess of free hydroxyl groups in compounds capable of increasing elongation, tear, traction, and as its base is vegetable fatty acid, increasing the thermal stability, which allows the compound an external and internal plasticizing effect with high resistance against thermal degradations. The present invention allows this plasticizer to be used in pvc articles in footwear, furniture, and stickers with no carcinogenic agent or agents that attack the environment.

STATE OF THE ART

[002] Primary plasticizers, with their high lubricity, allow greater interaction with intermolecular bonds of the polymer, in the specific case: pvc (polyvinyl chloride) . When we reach a balance in intermolecular forces known as Van der aals force, we conduct the reactivity of this interaction knowing the steps and effects that each group performs at the point of highest activity, in the case of polymer binding - chlorine, and in the case of more effective plasticizers, the bond with an aromatic ring.

[003] The derivatives obtained from phthalic anhydride have high reactivity, hardness, and resistance to tearing and stress due to this interaction.

[004] The cited patents seek to exalt the advantages of phthalic anhydride in this degree of reactivity, but does not consider the advantage of the excess of free hydroxyl, controlling the degradation by thermal stability provided by the fatty acid ester, the position of the epoxy group in the chain, and the balance reached with the molecular weight kept between 440 - 480.

[005] All of these factors, together with the plasticizing condition, demonstrate a control of physical properties totally dependent and determined by the incorporation conditions of the plasticizer.

[006] The present invention allows adjustments of physicochemical properties during the incorporation, according to the final product to be produced, i.e. the plasticizers have always been embedded in parts by the total polymer; properties such as stretching, resistance, and hardness depend on the type of plasticizer and mixtures as phthalate, or phthalates and epoxidized agents, phthalates and adipates, trimellitates with maleates, are provenly eliminated with the incorporation adjustments in this invention at the proposed level of reactivity.

[007] US 2010/0324185 Al GENG ET AL

[008] US 2012/0181057 Al CHAUDHARY ET AL

[009] US 2010/0256403 Al LAI ET AL

[0010] US 2009/0286896 Al ROH ET AL

[0011] US 3.079.412 CHANG, SS AND L.WEIDERMAN

[0012] US 4.876.304 MERTZ ET AL

OBJECTIVES OF THE INVENTION

[0013] Plasticizing polymer starting from 100% vegetable fatty acids to react with polyalcohols , or saturated aliphatic alcohols, or polyglycerols (derived from saponification or by-products of ethyl Ester (m) from bio- fuel fatty acid) via alcoholysis reaction, resulting a fatty acid ester with molecular weight (MW) greater than 300, hereinafter Fatty acid polyester, to react with a peroxide through a reaction known as epoxidation, to assist the compatibility and formation of hydrogen bonds with vinyl compounds in the production of footwear, textiles, rolled and flattened materials. When we reach the molecule of epoxidized fatty acid polyester to react with an aryl carboxylic acid, a toluilic or benzoic type acid, with metal catalysts to obtain a primary and a secondary activity on vinyl compounds, achieving unique properties, and allowing the formulator to use a single raw material to achieve all the properties of lubricity, adhesion, elongation, and physico-mechanical advantages attributed to Aryl Carboxylic Acid Epoxidized Polyester, which is environmentally friendly, non-toxic, non-harmful to the environment, and free of phthalates.

ADVANTAGES OF THE INVENTION

[0014] The Ecological Plasticizer herein has the same content of epoxy of an epoxidized primary plasticizer, the same number of hydroxyl of a adipate, sebacate, succinate polyester, but the resistance to thermal degradation, reduction/softening of vinyl-chloride bonds make possible, with natural products, to obtain an internal/external action to reduce the level of inclusion on the percentage of resin.

[0015] Reaction: PLASTICIZING POLYMER

HO- (CH₂)_n-OH

+

HO-C- (CR₉) -C-OR ± [HO (CH_?) -O-C- (CH₅) _x-C-Oj .

II II II II

O O 0 0

[0016] Reaction: EPOXIDIZED GLYCOLIC ARYL TRIESTER

DETAILED DESCRIPTION OF THE INVENTION

[0017] This invention has the technical innovation of introducing a reaction of 100% natural and ecological agents, obtained from renewable sources, creating a saturated chain triester with high branching, this compound allows the presence of an epoxy ring, providing a high compatibility by hydrogen bonds and Van der Waals forces, helping the external plasticity known as secondary system, then this epoxidized polyester react with arylcarboxylic acid, allowing this new system to be 100% compatibile with vinyl compounds, creating the compound internal and external plasticity, not being necessary to the use of additives or other plastxcizers to meet the expectations of physicochemical properties, as appended examples and tables .

[0018] Since it is a natural product, above 90%, the system is free from toxic agents, as well as features no carcinogen element or agent, according to studies conducted by the World Health Organization (WHO, reference below) , OSHA, EPA, and FDA with respect to the compounds. Thus meeting the expectations generated by products or compounds that use anhydride or phthalic acid, better known as phthalates .

[0019] Reaction: PHTHALATES

o o

[0020] Starting from an unsaturated vegetable fatty acid from corn, cotton, soybean, palm, peanut, rapeseed, castor bean, with carbonic distribution between C12 - C20, more specifically between C14 to C18. Characterized by the level of unsaturation .

[0021] Reaction: POLYESTER

R_j-OH + H-0-C-R₂ R₁-0-C--R₂ + H₂0

o o

[0022 ] 2. Starting from an alcohol derived from sugar cane, or starting from olefins, or starting from polyalcohols derived from esterification of vegetable origin that can be classified as mono, di, and triglycerides, hereinafter called glycerides.

[0023] 3. Starting from oxidizing agents, superoxidizing agents derived from sodium, potassium, and others. [0024] 4. Starting from arylcarboxylic acids whose natures are or not anhydrides of trimelitic, toluilic, benzoic and other types.

[0025] 5. Starting from raw materials derived from nontoxic plant origin that does not harm the environment and does not have phthalate compounds.

[0026] Starting from a fatty acid obtained from plant oils with C16 content below 30% and C18 content exceeding 70%, among them we highlight soybean, palm, cottonseed, groundnut, corn, castor bean, rapeseed, sunflower, and rice .

[0027] Reacted with a polyol obtained as a residue of transesterification of the fatty acid, esterification of fatty acids with (m) ethyl alcohol, saponification of vegetable oil.

[0028] By a reaction between a fatty acid and a polyglyceride known as alcoholysis reaction, obtaining a molar equivalent form, a fatty acid (tri) ester whose molecular weight is greater than 300.

[0029] React the fatty acid polyester with a peroxide through a reaction known as slow and gradual epoxxdation, and then obtain a fatty acid (tri) ester of epoxidized Vegetable fatty acid.

[0030] In direct line, react the Ester formed by the reaction between the fatty acid and the polyol with superoxidizing agents, obtaining the formation of epoxy chains .

[0031] The epoxidized vegetable fatty acid ester with plasticizing characteristics have properties known as secondary plasticization on vinyl compounds, which more than that action on the surface of the compound, enable us to increase its chemical resistance.

[0032] Under those conditions, react the epoxidized vvegetable fatty acid ester with aryl carboxylic acid, allowing the Plasticizer to meet environmental issues, increase its UV degradation, giving greater stability to the vinyl compound, achieving a low volatility with this reaction, withstand high temperatures, no changes in color, does not degrade or deform under conditions of excessive stress on the compound, does not generate any materials that may be harmful or toxic to the environment.

[0033] The polyester obtained from alcoholysis, subjected to epoxidation and subsequent esterification with aryl carboxylic acid, hereinafter called epoxidized fatty acid Triester esterified with aryl carboxylic acid, simply epoxidized glycolic aryl Triester free from phthalates.

[0034] Reaction: EPOXIDIZED GLYCOLIC ARYL TRIESTER

[0035] The industry of plasticizers , either elastomers industry or in plastic compounds industry, use lubricants since their beginnings.

[0036] The use of vegetable oils, fish oils, mineral oils dates back to the early twentieth century and since then tries to be updated with new agents, seeking to replace agents that are toxic to the contact of humans, initiating studies involving benzoates, then phthalates and later new generations of plasticizing polymers or copolyesters .

[0037 ] Esters of natural alcohols have become a reality in the last twenty years, due to the ease of reaction to create an epoxy chain, their use greatly contributed in reducing costs, external plasticization, known as secondary, allowing adjustments in physico-chemical properties using epoxidized fatty acids.

[0038 ] The issue that the use of epoxidized esters have induced the industry of compounds to the indiscriminate use in order to minimize costs and environmental issues created by the use of derivatives of phthalic anhydride as plasticizers . Thus the use of universal plasticizers with external and internal characteristics to PVC compounds is part of the formulators need for vinyl based compounds.

[0039] Polymeric plasticizers are well known and have established their advantages in their ease of handling and production, however in terms of cost, their use has always been controlled and therefore lower.

[0040] Using references as the PVC Handbook, the characteristics of plasticisers in terms of properties are those obtained by mixing and heating until the resins dissolve the plasticizer or the plasticizer dissolve the resins. The plasticized material is molded into a product of common use and cooled down. The desired goal of the plasticizer is that it reaches different physical and mechanical properties to meet the needs and be transformed into a flexible product, as the object of this patent.

[0041] To better understand the aspects presented here is important to reinforce plasticization concepts and mechanisms defined herein, as well as the characteristics that we want to deepen, concept of lubricity or full plasticization, whether primary or secondary (or external and internal) .

[0042] I.e., we determine the properties we want to achieve in the mixture on the PVC structure, as the expected result for an ideal plasticization.

[0043] Sears and Darby were who best portrayed aspects of the plasticization theory.

[0044] Objectively, we want to achieve specific properties, combining grafting with solvation, getting a Copolyester with high solvation and grafting.

[0045] Within the plasticizers, its purpose is to meet physical and mechanical properties described in example items and detailed in the state of art of this invention.

[0046] The plasticization lubrication theory defines that when we heat the system, the plasticizer ' s molecules enter in diffusion in the polymer, weakening polymeric interactions, which as we presented above, are called Van der Waals forces.

[0047] Our copolyester acts as a shield to reduce these polymer interactive forces (polymer-polymer) , which aids in the prevention of a rigid network in the polymer, since its function is to provide flexibility.

[0048] Therefore, we present the results obtained with the compounds via DSC (Differential Scanning Calorimetry) of the glass transition temperature (Tg) , since when we reduce the Tg of the PVC compound we are causing the polymer chains to move rapidly, increasing the flexibility of the compound, softening and stretching, which we defined as grafting and solvation. [0049] The gel theory considers the plasticized polymer not as a solid or liquid polymer, but rather as an polymer in intermediate state, which could be explained if we consider a smooth three-dimensional network of weak secondary binding forces. That is, we could see the tension achieved with grafting and solvation that we produced with the esterification of epoxidized Ester aryl carboxylic acid .

[0050] Under "tests", we present the stretching and flexibility by tensile and strength, tear tests, resilience, and compound softening tests.

[0051] Finally the theory of free volume was used to exemplify stiffness and hardness, considering the internal space within the polymer that we detected through its movement (internal fill) caused by the consolidation of its structure, either (delete) comprising its characteristics when heated under conditions of polymer crystallization. Such characteristics were presented in the interpretation of the DSC curve of the polymer plasticized with copolyester and compared to other types of plasticizers that individually have the concepts of grafting or solvation .

[0052] (See DSC Tables) .

[0053] Thus we clarify how the copolyester is fixed to the polymer structure ends by adding the chains that allow greater flexibility and stretching. (See table of results)

[0054] The copolyester allows the thermoplastic, specifically PVC, if its crystalline part is affected, to directly affect its solvation when grafting its ends, as the results achieved in its physical and mechanical properties, just modifying its amorphous part.

[0055] These properties can only be achieved when we calculate the optimal level of inclusion of copolyester on PVC resin, demonstrated by examples, then we realize that in amounts with less than 15 parts of resin, we only actuate in weak interactions, but in quantities exceeding 35 parts, we reached excess of solvation without grafting, so we have high stretching, however, we began to lose flexibility and softening.

[0056] The copolyester of the invention meets the polar and nonpolar characteristics necessary to the efficiency of plasticizers in polymeric compounds.

[0057 ] The present invention presents this balance through its physical and mechanical results, as well as thermogravimetric assays of molecular weight distribution by GPC, allowing to demonstrate the proper compatibility and solvation of the compound before and after plasticized, herein presented by IR spectrophotometry charts with characteristic wavebands of polar and nonpolar groups on the PVC compound and these charts compared to plasticizers with specific concepts, for solvation or grafting.

[0058] The results presented in experiments seek to compare commonly used plasticizers, plasticizers with different performance and special plasticizers, and thus introduce the concept of solvation and grafting as a complementary concept to the properties, thus defining the copolyester as an agent of flexibility and solvation.

[0059] The objective of this invention is to present a plasticizer with polymer characteristics, low molecular weight, high compatibility with vinyl compounds, and introduce families of plasticizers with internal and external characteristics regarding lubricity with full compatibility and solubility with the thermoplastic.

[0060] Thus the interest of the industry for conventional chemical compounds changed in the sense of having natural alternatives, which have become a requirement in the last 5 years, in order to meet environmental prerogatives, free from volatile organic compounds (VOC) , disposal of pollutants and toxic agents (PAHs) , and the increased consumption of natural and renewable sources.

[0061] Fatty acids (chart below) have in their composition for this invention their highest concentration in the range C16 - C18.

[0062] The fatty acid undergoes a process of isomerization (patent) reaching an acidity index range of 180 - 190 mg OH/g.

[0063] The mixture of those fatty acids rich in fractions C16 - C18 allows us to separate them in palmitic, palmitoleic, stearic, oleic, and linoleic acids.

[0064] Since it is an esterification by condensation, it is common to use acid catalysts, getting the advantage of working at low temperatures with high yield production.

[ 0065] Acid catalysts of sulfuric acid type and their modified derivatives, p-toluene sulfonic acid, o-xylene sulfonic acid, methane sulfonic acid, fall into this class of catalysts.

[0066] The use of these catalysts makes the fatty acid ester to not have characteristics of high lubricity and internal plasticization reached by derivatives of phthalic anhydride, whose nature of benzene ring allows greater solubility and compatibility, reaching an elongation and tensile and tear strength much higher than those obtained by DOA with catalysts of this family (see table) .

[0067] The use of catalysts guiding the introduction of the metallic compound allows us to make use of metals such as lithium, potassium, tin, and vanadium in order to reach physico-chemical and physical-mechanical properties equal or superior to those obtained by compounds with the use of derivatives of phthalic anhydride. [0068] The nature of arylcarboxylic acid allows to better distribute the carbon in the molecular structure (as reaction) , which enables the excess alcohol to reach the appropriate properties beyond the guidance given by the catalysis system.

[0069] The reaction order obtained in this plasticizer is another factor featuring, in PVC compounds, a high elongation, which ultimately allows its use in scales with a significant increase in production, due to the elimination of more flow agents.

[0070] This invention determines esterification steps, the final characteristics of the plasticizer, allowing to reach a polymeric plasticizer of low molecular weight and primary and secondary characteristics in only three steps. ALCOHOLYSIS

[0071] The principle of alcoholysis was widespread by the paint industry for obtaining resins known as alkyd resins. This transesterification mediated by metal catalysts is carried out under conditions of high temperature and controlled by turbidity and viscosity characteristics .

[0072] After the steps are concluded, we configure the Ester obtained with the reaction of a glyceride and a vegetable fatty acid.

[0073] The polyol may be a glycide as sorbitol, xilito, mannitol, molasses, sucrose, corn syrup, saponification residues, esterification residues of methyl alcohol and vegetable fatty acids, such as soybean, corn, cottonseed, palm, castor seed, among others.

[0074] In the ester obtained by alcoholysis of a polyol vegetable oil (polyalcohol) , we introduced a super oxidizing agent in peroxide form in the resulting fatty acid, to introduce the epoxy ring.

[0075] The purpose of the reacting following the alcoholysis is to obtain an epoxy function that enables the plastic compound to reach tear and elongation resistance in actions carried out on its surface.

[0076] Thus we achieved plasticization degrees in the compound of external or secondary order, also known as external plasticization.

[0077] Reaction: PLASTICIZING POLYMER

HO- (CH₂ ) _n-OH

+

HO-C- (CH₂ ) -C-ΟΗ ^ [HO (CH₂ ) -O-C- (CH₂ ) _x-C-0] _t II II II II

O O 0 0

[0078] Reaction: EPOXIDIZED GLYCOLIC ARYL TRIESTER

[ 0079] Once the epoxidized Esther is obtained, it is necessary to complement its characteristics taking the epoxy ring as a reactive site that allows grafting, reacting with carboxylic acids, aryl carboxylic, carboxylic diacids, acid anhydrides, isocyanates, amines and amides, etc .

[0080] The reaction of the epoxidized ester with natures such as maleic anhydride, benzoic acid, and succinic acid allows us to achieve a compound with the same characteristics of external and internal plasticization, according to the results.

[0081] Thus we reach a plasticizing polymer with low molecular weight and very similar to primary plasticizers, facilitating handling and production control of laminated and flattened material.

[ 0082] Patent citations and use of techniques to obtain epoxidized, phthalates, and benzoates.

ADVANTAGES OF THE TECHNIQUE FOR PRODUCING ECOLOGICAL PLASTICIZERS . COMPARISON WITH ECOLOGICAL PLASTICIZERS , EPOXIDIZED, PHTHALATES AND BENZOATES .

[0083] Mounting the property results table.

Examples :

[0084] 1 mol of corn oil with 2 moles of glycerol react under action of a metal catalyst (based on zinc, tin, magnesium, or lithium) while maintaining the temperature between 180 - 300°C, more precisely between 200 - 260°C, we have the formation of 3 moles of monoacylglycerol.

a. We react the 3 moles of monoacylglycerol with

hydrogen peroxide at a ratio of 1 mol, controlling the epoxy eguivalent up to a level exceeding 800.

b. We react the epoxidized triester with toluilic acid in 3:2 ratio, controlling the temperature in the range 180 - 220 °C, obtaining epoxidized glycolic aryl triester (see results)

[0085] 1 mole of rapeseed oil with 2 moles of glycerol reacted under action of a metal catalyst while maintaining the temperature between 200-260 °C. We achieve the formation of 3 moles of monoacylglycerol.

a. We react the 3 moles of monoacylglycerol with hydrogen peroxide at a ratio of 1 mol, controlling the epoxy equivalent up to a level exceeding 800. b. We react the epoxidized triester with toluilic acid in 3:2 ratio, controlling the temperature in the range 180 - 220°C, obtaining epoxidized glycolic aryl triester (see results)

[0086] 1 mole of soybean oil with 2 moles of glycerol reacted under action of a metal catalyst while maintaining the temperature between 200 - 260°. C Reached the formation of 3 moles of monoacylglycerol .

a. We react the 3 moles of monoacylglycerol with hydrogen peroxide at a ratio of 1 mol, controlling the epoxy equivalent up to a level exceeding 800.

RESULTS

RESULTS IN PVC COMPOUNDS

Shore d hardness assay in compound parts after 3 minutes (value found and maximum) . EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 PARTS 64 - 70 65- 73 68-77 PARTS 50 -64 52 - 64 54 -68 PARTS 45 - 54 48 - 60 45 - 60

Claims

1 . " PROCEDURE FOR OBTAINING PLASTICIZING POLYMER" , characterized by obtaining an environmentally friendly plasticizer through condensation polymerization reactions, alkylation and epoxidation, in order to achieve a low molecular weight, low viscosity plasticizer with very high flash point, allowing the PVC polymer to soften vinyl- chloro bonds, allowing both primary and secondary plasticization .

2. " PROCESS " , characterized by reactions and steps herein presented for obtaining an ecoloical plasticizer have as their innovation the inclusion in the condensation polymerization step of the balance of the aryl chain across the epoxy group without changing the advantage of the fatty group.

3 . " PROCESS" according to claim 2, characterized by in the steps of reactions of composition of the epoxidized glycolic aryl triester plasticizer, the balance of temperature and pressure conditions coordinated by the action of a polymerization catalyst, allowing thus, by the temperature, to guide and maintain the epoxy group; the epoxidized glycolic aryl triester plasticizer presents the innovation of its polymeric structure maintaining a low molecular weight, allowing the prevention of degradation by external actions as light and heat, allowing the maintenance and increase of physical-mechanical properties of the compound that uses pvc polymer, besides reducing the inclusion of stabilizers and the effective mass of plasticizer for softening resin.

4. "PRODUCT" according to claim 3, characterized by the product obtained epoxidized glycol aryl Triester provide the following basic reaction: