CN1723227A - Castor oil/epoxidized soybean oil based elastomeric compositions - Google Patents

Abstract

Elastomers are formed from castor oil and/or ricinoleic acid estolides and a polyester formed form an epoxidized vegetable oil such as ESO and a polycarboxylic acid such as sebacic acid, optionally in the presence of a peroxide initiator, or include crosslinked reaction products derived from ricinoleic acid or castor oil estolides, epoxy group-containing compounds such as epoxy resins and/or epoxidized vegetable oil, epoxy hardeners such as polyamine and polycarboxylic acid hardeners, thermally activated free radical initiators such as peroxides, and optionally but preferably include fillers such as limestone or wood flour. The elastomers can be prepared using a two-step, solvent-less procedure at elevated or ambient temperatures. These predominantly all-natural elastomers have physical properties comparable to conventional petroleum-based elastomers and composites and exhibit good flexibility, resiliency, abrasion resistance and inertness to hydrolysis. The resulting elastomers display good mechanical strength and resiliency, are resistant to abrasion and hydrolysis, and can be processed into sheet materials, which makes them attractive a floor covering components.

Description

Viscotrol C/oil/epoxidized soybean oil based elastomeric compositions

The present invention relates to elastomer material by Viscotrol C and/or ricinolic acid polylactone and polyester cross-linking are formed, described polyester is by making the reaction of the material that contains epoxy group(ing) such as epoxidized soybean oil and poly carboxylic acid and form and relating more particularly to comprising the resiliently-mounted floor material at interior ground finishing coat.

Most of flooring materials are prepared by polyvinyl chloride usually.Use for flooring material, PVC contains a large amount of terephthalic acid ester plasticizer (based on PVC greater than about 30wt%) usually to produce competent flexible and shock strength, typically by hot mechanically mixing PVC, terephthalic acid ester plasticizer, filler such as lime carbonate and additive, then prepare required floor sheet material by calendering process, thus the preparation flooring material.

Elastomer material that is derived from ricinolic acid and/or Viscotrol C and the product that comprises this elastomer material are disclosed.By the pet reaction that makes Viscotrol C/ricinolic acid polylactone (ricinoleic acidestolide) (intermediate polyester) and form, thereby form this polymkeric substance by epoxidized soybean oil (ESO) and poly carboxylic acid such as sebacic acid.The two-stage cure technology for preparing this elastomer material is also disclosed.

Form Viscotrol C/ricinolic acid polylactone by the esterification that involves hydroxyl, carboxylic acid and/or ester functionality in ricinolic acid and/or the Viscotrol C, randomly be included in crosslinked between the vinyl in the ricinolic acid part in the main polymer chain, wherein said main polymer chain is with causing formation by the catalytic free radical of thermal activation radical initiator (crosslinking catalyst).

The polyester that forms with epoxidized vegetable oil and poly carboxylic acid mainly involves hydroxyl and the carboxylic acid group that carboxylic acid and epoxy reaction form ester bond and the formation of dissociating by epoxy group(ing) and reacts the formation ester bond.

Dissociating of Viscotrol C/ricinolic acid polylactone and polyester ester bond involves the formation ester bond, and forms optional extra crosslinked by adding extra poly carboxylic acid, polyamine compounds, polyacrylic ester or other linking agent.Polyamines is by forming amido linkage and can be by forming the amine key with epoxy reaction with carboxylic acid group reaction.This method obtains the polymer molecular structure as interpenetrating polymer networks (PPN) described herein.In some embodiments, use great majority to be derived from the biodegradable component of the material of nature existence, produce elastomer material with simple, effective, eco-friendly method.Naturally the material of Cun Zaiing comprises the soya-bean oil that nature exists, and especially Viscotrol C and derivative thereof are as sebacic acid.Polyacrylic ester reacts with the two keys that exist in polylactone and/or polyester, cause crosslinked, thereby cause forming carbon-carbon single bond.

This method promotes between the straight chain polyester that forms by polymerized castor oil and/or ricinolic acid polylactone and epoxide activator and and by interchain or chemical crosslink reaction between the relative more complicated polyester that makes epoxidized vegetable oil such as ESO and polyacrylic acid reaction generation.With these delay cross linkings reaction (postpone to be meant in some sense at two kinds of polyester before the crosslinked coupling, formed this two kinds of polyester earlier), between two very big polymer architectures, form three-dimensional interpenetrating polymer networks (PPN) structure.This generation has required physical strength and flexible polymkeric substance, and this polymkeric substance can for example be used to form the elastomer sheet flooring material.

In order to ensure forming the PPN structure, can be randomly in the presence of the peroxide activator of thermal activation, at first pre-polymerization Viscotrol C and/or ricinolic acid form heavy-gravity liquid polylactone mixture.Ricinolic acid/ricinolic acid prepolymer is the mixture of straight chain, ring-type and slight crosslinked polyester construction.Also can there be ricinolic acid dimer and tripolymer, lactone, lactide and other simple ester.When in the presence of appropriate catalyst, accepting high temperature, at Viscotrol C/ricinolic acid intramolecularly generation self-condensation reaction, the hydroxyl of one of them molecule and the carboxyl reaction of another molecule, the rest may be inferred forms the straight chain ester bond.

Simultaneously, but form two keys of Viscotrol C molecule and the extra key of formation in castor oil soap by peroxide activated free radical reaction also attack.Randomly, can use polyacrylic acid (comprising dicarboxylic acid), form slight crosslinked castor oil soap/polylactone.In the forming process of PPN structure, these Viscotrol C/ricinolic acid polylactone serves as intermediate, for second polymkeric substance to the further polyreaction of (polymer pair) (by making polyester of forming of epoxidized vegetable oil and polyacrylic acid reaction).

Advantageously, by naturally occurring vegetables oil, it is right to form second polymkeric substance as the functional derivative of epoxidized soybean oil (ESO) and sebacic acid (it also can be derived from Viscotrol C).Can use ESO, for example in final PPN structure, add the potential crosslink sites and as " natural " standby surrogate of petroleum base organic monomer.High epoxy value in ESO (usually＞6%) guarantees to obtain competent reaction site to add on this molecular structure or to generate the PPN structure.In addition, because ESO is natural and reproducible raw material, so its use has increased in the intravital natural constituents of the elasticity that is generated.In one embodiment, in the presence of Viscotrol C/ricinolic acid prepolymer, by placing polylactone, poly carboxylic acid and contain the material of epoxy group(ing) in reaction vessel, it is right to form second polymkeric substance on the spot.

Can produce elastomerics described herein by the method simple, that effective environmental is friendly.Rubber-like elastic body can be used as top coat for example ground and wall coating and similar sheet material.In addition, they can be molded as non-sheet material and are used for motor vehicle and other and use.

The two-stage cure method of preparation elastomer material is also disclosed.This method obtains being called as the polymer molecular structure of interpenetrating polymer networks.With the method simple, that effective environmental is friendly, use and be derived from the natural biodegradable component that has material, produce this elastomer material.

The first step of this method comprises by ricinolic acid and/or Viscotrol C and prepares prepolymer.This prepolymer comprises the straight chain of ricinolic acid and/or Viscotrol C, lactone, lactide, simple ester and higher molecular weight or the dimer and the tripolymer of cyclic ester compound.Enzyme catalysis and/or acid catalysis be can use, typically under the condition that increases temperature, progressively dimerization, trimerization and/or the polymerization of ricinolic acid and/or Viscotrol C realized.In either case, when hydroxyl and carboxyl when forming each ester bond, form water molecules as by product.Yet, when using enzyme catalysis, mainly be the straight chain polyester because the stereochemical specificity of enzyme and zone select control to cause the prepolymer polylactone.Randomly, dicarboxylic acid such as sebacic acid, tricarboxylic acid such as citric acid, and/or poly carboxylic acid can react formation polylactone prepolymer with ricinolic acid and/or Viscotrol C.

This polylactone can be further and the catalyzer (crosslinking catalyst) of the generation free radical of thermal activation, as the peroxide activator reaction, makes the two keys in prepolymer master intrachain ricinolic acid part crosslinked.Can randomly add the linking agent such as the Vinylstyrene that contain alkene, to increase degree of crosslinking.Yet in one embodiment, two keys in ricinolic acid are not crosslinked, opposite to hydroxyl, amine, carboxylic acid and/or thiol functionalities in prepolymer, contain the reaction of the compound of epoxy group(ing) and/or linking agent such as polyamines, poly carboxylic acid, mercaptan, phenols etc., in interpenetrating(polymer)networks, take place crosslinked.

By making carboxylic acid or the hydroxyl on the ricinolic acid part in the main polymer chain, perhaps prepare the carboxyl on employed other carboxylic moiety of polylactone, with the compound reaction that contains epoxy group(ing), make the compound that contains epoxy group(ing) such as Resins, epoxy and/or epoxidized vegetable oil conjugation to the polylactone prepolymer.Use conventional epoxy curing agent then, as polyamines, poly carboxylic acid, phenols, mercaptan and analogue, crosslinked unreacted epoxy groups.Amido when existing, also can react the formation amido linkage with the carboxylic acid group.

Therefore, curing reaction can be considered the binary crosslinking reaction that bulk reaction at the interface zone place adds auxiliary carboxyl-amine reaction.Crosslinked epoxy group(ing) forms interpenetrating polymer networks, involves the structure that crosslinking reaction that the free radical in the main intrachain double bond structure of ricinolic acid polylactone causes forms interregional chemical bonding simultaneously simultaneously.In addition, when having excess amine (i.e. the consumption that requires greater than sclerosis garden carboxyl), amido can with the carboxyl reaction on the ricinolic acid molecule, the epoxy consistency mutually that this can improve most of ricinolic acids and grow.The result is elastic binary interpenetrating polymer networks structure.

Required effect is to produce independently crosslinking reaction on across the interface zone between the different homopolymer.A kind of network structure can (maybe be worked as and use other epoxy curing agent by the crosslinked of the initiation of diamines in Resins, epoxy, similar crosslinkedly during as mercaptan, phenols and carboxylic acid) and generate, and the radical crosslinking of another crosslinking structure by the peroxide-induced of unsaturated double-bond in the ricinolic acid polylactone form.In addition, if use excessive polyamines stiffening agent, then between ricinolic acid and diamines, carboxyl-amine reaction is possible, and this reaction promotes extra interface stability and structure.

In one embodiment, by mixing all components simultaneously, partially polymerized reactive ingredients, then when forming interpenetrating(polymer)networks, this material of polymerization more completely, thereby preparation elastomer material.Can there be filler, as elastomer material other additive commonly used of Wingdale and/or wood powder and preparation filling.Advantageously, in polyreaction, add filler afterwards at first step (promptly forming polylactone).Having filler between 0 consumption and, when the time as the component of sheet material flooring material typically existing between about consumption of 40 to about 60wt% to about 90wt% polymer materials.

All polylactones, the compound that contains epoxy group(ing), crosslinking catalyst and stiffening agent reaction, formation have the elasticity interpenetrating(polymer)networks of required tensile strength and elongation performance to be used as sheet goods and the other products that wherein uses elastomer material routinely.The example of product comprises top coat such as floor and wall coating and similar sheet material, with the material that becomes non-sheet-form to form by the molding resilient material, comprising the material that uses in motor vehicle and other application.

In one embodiment, stir ricinolic acid polylactone prepolymer, the free radical catalyst of Resins, epoxy and more a spot of polyamines stiffening agent and thermal activation, gentle exothermic polymerization reaction takes place in about 10 minutes of methylethylketone (MEK) superoxide (10min) simultaneously.Then, in one embodiment, with the filler of aequum, for example at most 60wt% are incorporated in this reaction mixture and packing material helps to weaken the skew of any autocatalysis heat release.Stir complete reaction mixture about 10 minutes (10min) in addition, this mixture is prepared to be used for casting, molding or or to form final product structure this moment.The example that processing is selected comprises calendering, mouthful pattern coating, extrusion molding and analogue.Afterwards, make mixture carry out extra curing reaction, can quicken described curing reaction by heat.

Elastomer material described herein is interpenetrating polymer networks (PPN), promptly contains the polymkeric substance of two or more networks, unless described network interweaves and typically covalent bonding and chemical bond rupture each other to small part on molecular level, otherwise can not separate.Elastomer material contains the part that is derived from Viscotrol C and/or ricinolic acid and also can comprise and be derived from poly carboxylic acid, epoxidation or or the part of functionalization vegetables oil and/or polyamines.

With reference to following explanation, will understand elastomer material better, prepare the employed polyester of this elastomer material, contain the product of this elastomer material and prepare the method for this elastomer material.

I. prepare the employed component of elastomer material

A. Viscotrol C and/or ricinolic acid polylactone

The initial step that involves in the preparation elastomer material is preparation Viscotrol C and/or ricinolic acid polylactone or prepolymer.Viscotrol C is many places in the world, the natural oil that exists in the seed as India, Brazil and the Chinese castor-oil plant beans of growth in large quantities.In all seed oils, Viscotrol C is unique, because it is main (＞90%) by hydroxyl, unsaturated, the important oil of unique commerce that C18 lipid acid is formed, it is called as ricinolic acid, is have two keys on the 9-10 carbon location and have the acid of 18 carbon of hydroxyl on the 12nd carbon atom.The reactive group that Viscotrol C can participate in potential polyreaction is given in the combination of this uniqueness of the two keys of hydroxyl and unsaturated carbon.By careful control hydrolysis refined caster oil, form the ricinolic acid glycerine of by product (and as).The ester structure that also can contain in one embodiment, dimer, tripolymer and Geng Gao homologue as the ricinolic acid of parent material.

When superoxide is used as crosslinking catalyst in the polylactone prepolymer is synthetic, the liquid polylactone mixture that forms by Viscotrol C and/or ricinolic acid comprise by the straight chain that dissolves each other, ring-type and lightly crosslinked (be insufficient crosslinked, so that the polylactone mixture is a solid) polyester portion, described polyester portion is formed by the progressively esterification of two keys and optional chain polymerization.

In addition, unreacted Viscotrol C itself can form dimer and/or tripolymer or provide further reaction site for monomer crosslinked with epoxidation.Under the situation of these polyester prepolyers, high relatively molecular weight and higher cross-linking density may be important concerning successfully preparing elastomer material.In general, viscosity at ambient temperature finds it is useful greater than the prepolymer of about 3000cps.

Form ester with enzyme method

Can use acid catalyst or enzyme catalyst esterification hydroxyl and the carboxylic acid group in ricinolic acid.Under the reaction conditions of gentleness, use the synthetic environment-friendly method of polymkeric substance of isolating enzyme catalyst to receive a lot of science concerns as polymer production.For example, use lipase-catalyzed dose, by the aliphatic polyester of various monomer synthesizing biological degradables.In addition, can in different media (comprising moisture and organic radical this two kinds of systems and solvent-free system), carry out enzymatic polymerization.In one embodiment, in non-water that does not comprise organic based solvent and solvent-free medium, carry out enzymatic polymerization.

About any enzymatic polymerization process, must obtain producing the synthetic microorganism of required polymkeric substance with enzyme.Although involve only normal experiment, this system of selection can require screening, especially optimizes enzymic activity, and in the case, described enzymic activity is based on the selectivity of ricinolic acid.For example, the lipase that is derived from Candida Antarctica B is a kind of effective esterifying catalyst that can produce the ricinolic acid polylactone.Serviceable time is differentiated enzyme distribution technique subcontrol whipping characteristic, this is because can be in polymerization under the situation of not using solvent and the viscosity that advantageously realizes polymerization and reaction mixture under the situation of not using solvent along with (by esterification) polymerization is carried out increasing.

In enzyme-catalyzed polymerization suitable time period under suitable temperature, for example after following 72 hours of the room temperature, the heavy-gravity liquid prepolymer can be thought light brown.After the enzyme-catalyzed polymerization operation, prepolymer composite typically comprises straight chain and cyclic simple ester or polylactone, adds dimer, tripolymer, higher homologue and unreacted ricinolic acid in starting raw material.The variation of mixture apparent viscosity size is the sign that molecular weight increases and prepolymer forms, and this is important parameters in the preparation of elastomer material.If too low with apparent viscosity after the enzymatic polymerization, then formed prepolymer can only be used as softening agent, or when further solidifying, cause the material of soft embrittlement.Just because of this, it may lack desired mechanical property: some use required toughness and flexible.The molecular weight of prepolymer or apparent viscosity should be high enough to successfully as parent material, have requisite mechanical property and a flexible elastomerics with what preparation was used in flooring compositions.In general, viscosity at ambient temperature finds it is useful greater than the prepolymer of about 3000cps.

Form enzyme with acid catalysis

If use acid catalyst, then in fact catalyzer can be the Bronsted acid or the Lewis acid of energy catalytic esterification.Preferably, catalyzer is solvable or can disperse at least in reaction mixture.Tosic acid (p-TSA) is the example of appropriate catalyst.

In esterification reaction process,, can use vacuum or decompression to change into the polyester polylactone to promote to remove the water that forms by esterification and improve ricinolic acid no matter use chemistry or enzyme enzymatic synthesis condition.

Can make the reaction of Viscotrol C and/or ricinolic acid by under sufficiently high temperature, thereby obtain the straight chain polyester, wherein the carboxyl reaction of the ricinolic acid in hydroxyl in the ricinolic acid or the Viscotrol C and another molecule forms ester bond.In addition, when causing with superoxide, also can radical polymerization take place at the unsaturated double-bond place, described polymerization connects adjacent Viscotrol C/ricinolic acid molecule effectively.Therefore, polymerizable Viscotrol C and/or ricinolic acid are produced the thick liquid that comprises polylactone, and described polylactone serves as the intermediary material of further polyreaction.

The free radical catalyst of thermal activation

Although the formation ester bond, the radical polymerization that can cause with the radical initiator (crosslinking catalyst) of thermal activation by two or more pairs of keys in the coupling main polymer chain, forms extra crosslinked in Viscotrol C/ricinolic acid polylactone.Crosslinked adjacent ricinolic acid molecule or other component in the Viscotrol C of connecting effectively of unsaturated double-bond.Therefore, polymerizable Viscotrol C and/or ricinolic acid are produced the thick liquid that comprises polylactone, and described polylactone serves as the intermediary material of further polyreaction.

Can use the free radical catalyst of any thermal activation of the olefin group that exists in crosslinked Viscotrol C of energy or the ricinolic acid (and/or material of other olefine-containing group).This catalyzer is that skilled those skilled in the art is known, with comprise for example one or more (1) 2,5-2, (2) 1,4-two-(2-t-butylperoxy sec.-propyl) benzene, tert-butyl peroxide cumyl, (3) di-t-butyl peroxide, (4) 2,4,4-tri-methyl-amyl-2-hydroperoxide, (5) diisopropyl benzene list hydroperoxide, (6) cumene hydroperoxide and (7) Diisopropyl azodicarboxylate (AIBN).In one embodiment, 2 of its commodity Triganox 101-45B by name, 5-2 superoxide is as catalyzer.

Can advantageously at room temperature activate superoxide, for example methylethylketone (MEK) superoxide as radical polymerization initiator.Other superoxide such as di-t-butyl peroxide, dibenzoyl peroxide and dicumyl peroxide can at high temperature be used for solidifying.In one embodiment, based on composition weight, use the content of about 0.1-about 5%.In another embodiment, also can use and under 25 ℃, demonstrated 10 hours or other superoxide of transformation period still less.In yet another embodiment, use the mixture of superoxide with different activation temperatures.

In the preparation elastomer material, the molecular weight of prepolymer polylactone and the polymerization degree may be important consideration.In one embodiment, the free radical catalyst of thermal activation, as superoxide, and acid catalyst, as the combination of p-TSA, the polymerization that activates Viscotrol C and/or ricinolic acid effectively forms polylactone.

When superoxide is used as crosslinking catalyst in the polylactone prepolymer is synthetic, the liquid polylactone mixture that generates by Viscotrol C and/or ricinolic acid comprise the straight chain that dissolves each other, ring-type and lightly crosslinked (be insufficient crosslinked, so that the polylactone mixture is a solid) polyester portion, described polyester portion is formed by the progressively esterification of two keys and optional chain polymerization.

In addition, unreacted Viscotrol C itself can form dimer and/or tripolymer or the further reaction site monomer crosslinked with epoxidation is provided.Under the situation of these polyester prepolyers, high relatively molecular weight and higher cross-linking density may be important concerning successfully preparing elastomer material.In general, viscosity at ambient temperature finds it is useful greater than the prepolymer of about 3000cps.

The linking agent that contains alkene

In one embodiment, there is the linking agent that contains alkene, as Vinylstyrene and other diolefine and/or polyolefine, to provide further crosslinked.

Poly carboxylic acid

Except Viscotrol C and/or ricinolic acid, also can use one or more polyfunctional carboxylic acids, form lightly crosslinked polylactone prepolymer.In the forming process of PPN structure, these polylactone prepolymers serve as and the intermediate of second polymkeric substance to further polyreaction.Poly carboxylic acid has the general formula of following type:

R-(COOH) _x

Wherein x be equal to or greater than 2 and R equal aliphatic, alicyclic or aromatics part.In one embodiment, poly carboxylic acid has 2-14 carbon atom, for example oxalic acid, succsinic acid, fumaric acid, propanedioic acid, toxilic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, brassylic acid, thapsic acid.Can separate (fussion) by the alkali fusion of Viscotrol C and produce sebacic acid (a kind of dicarboxylic acid) and sebacic acid can be preferred for generating elastomer material described herein.

In yet another embodiment, poly carboxylic acid is trifunctional acid or the hydroxycarboxylic acid with 2-14 carbon atom.The example of this carboxylic acid comprises oxyacetic acid, lactic acid, 2-hydroxybutyric acid, 2-hydroxy-iso-butyric acid, 2-hydroxycaproic acid, citric acid, toxilic acid and 2-hydroxyl isocaproic acid.The trifunctional acid citric acid is a preferred cross-linking agents, because it is the natural compounds of finding in all Citrus.

Randomly, also can add organic alcohol, advantageously dibasic alcohol or polyvalent alcohol are produced the polylactone prepolymer.Also can use the organic amine that contains the amide functionality.Optionally, can use the radical polymerization than low degree of unsaturated double-bond, preparation polylactone prepolymer.

B. the polyester that forms by material that contains epoxy group(ing) and poly carboxylic acid

In the presence of polyamines, by making the material that contains epoxy group(ing), mainly be epoxidized vegetable oil such as ESO, with the poly carboxylic acid reaction, thereby form employed other prepolymer polyester material of preparation Viscotrol C synthetic polymer network (PPN).Below will describe the component that contains epoxy group(ing) in this reaction in detail; Abovely poly carboxylic acid has been described in conjunction with Viscotrol C/ricinolic acid polylactone.Can in the presence of polylactone, form polyester on the spot.

Epoxidation or or the material of functionalization

Can as Resins, epoxy and/or epoxidized vegetable oil,, form second polyester prepolyer by making the compound that contains epoxy group(ing) with the poly carboxylic acid reaction.Can with Viscotrol C/ricinolic acid polylactone in carboxylic acid and/or the reactive epoxy group(ing) and/or the carboxylic acid group of hydroxyl reaction, further crosslinked gained prepolymer.In one embodiment, by comprising the functionalization vegetables oil, form the intermediate polyester as the reaction mixture of epoxidized vegetable oil, so as except by provide in the alkene functionalities on the Viscotrol C monomer crosslinked, also provide epoxy or other functional group for further crosslinked.

In another embodiment, polylactone and the compound that contains epoxy group(ing), as Resins, epoxy and/or the reaction of epoxidised vegetables oil, formation can be with the further crosslinked material of reactive epoxy group(ing).In one embodiment, by comprising Viscotrol C and/or ricinolic acid and functionalization vegetables oil, reaction mixture as epoxidized vegetable oil, form intermediate polyester (polylactone), so that except by provide in the alkene functionalities on the Viscotrol C monomer crosslinked, also provide epoxy or other functional group for further crosslinked.

Epoxidized vegetable oil is by the crude vegetal of chemical modification.A kind of such functionalization vegetables oil is epoxidized soybean oil (ESO).A polycarboxylic example is a sebacic acid, and it also can be derived from Viscotrol C.ESO environmental friendliness and biodegradable.ESO has several purposes.ESO can improve the flexible of final polymeric articles and by epoxy group(ing) and other reactive component at ESO, form chemically crosslinked as polyamines or poly carboxylic acid ester bond by serving as the softening agent of rigidity epoxy phase, can improve the physical strength of final polymkeric substance.Use ESO to increase the composition of the natural constituents of final PPN elastomer product.The functionalization vegetables oil also increases the potential crosslink sites in the final PPN structure, and serves as " natural " standby surrogate that at least a portion also can be used for forming the petroleum base organic monomer of intermediate polyester.High oxirane value (usually＞6%) guarantees to obtain competent reaction site to be added in the aromatic structure or to generate the PPN structure in ESO.In addition, because ESO is natural and reproducible raw material, so its intravital natural constituents of elasticity of using increase to be generated.Soya-bean oil based products (comprising ESO) tends to nontoxic relatively, biodegradable, and it is not lasting to tend in environment, and comes from natural reproducible resource.

Epoxide base in ESO can react with poly carboxylic acid such as sebacic acid, forms the polyester key.At the epoxide base of ESO base and the reaction of carboxylic acid group's ester bond is progressively growth response.On the vegetables oil molecule, there are three or more epoxy group(ing), when reacting, cause forming network with polyacid.In addition, the hydroxyl that in reaction process, forms and be present in the possible position that hydroxyl on the Viscotrol C main chain provides further reaction and PPN to form.

Resins, epoxy also can be in conjunction with epoxidized vegetable oil, or uses in conjunction with Viscotrol C polylactone (castor oilestolide) or ricinolic acid polylactone.The diglycidylether or the DGEBA Resins, epoxy of the dihydroxyphenyl propane that in one embodiment, use polyfunctional epoxy resin, is purchased.In an example, the content with about 3-about 15% of composition weight uses DGEBA.In another example, Resins, epoxy is four sense Resins, epoxy four glycidyl group diaminodiphenylmethane (TGDDM), and uses with the content of about 3-about 15% of composition weight.

The molecule and the poly carboxylic acid that contain epoxy group(ing) react under suitable temperature and pressure, make the crosslinked and formation intermediate polyester of parent material.

Linking agent

Epoxidized vegetable oil (after reacting with poly carboxylic acid) provides crosslinkable site, by making epoxy group(ing) in the epoxidized vegetable oil and carboxylic acid group and/or the hydroxyl reaction in Viscotrol C/ricinolic acid polylactone prepolymer, these crosslink sites can be used for crosslinked and form the PPN structure.

Can use the employed any suitable polyamines of crosslinked (sclerosis) Resins, epoxy.The example of suitable polyamines linking agent comprises alicyclic diamine, as (1) isophorone diamine, (2) 1,2-diamino-cyclohexane, (3) double mutual-amido cyclohexyl methane, with 1,3-BAC hyperergy alicyclic diamine, (4) triethylene glycol diamine, (5) 1,5-diamino pentane (cadaverine) and (6) 1,4-two amido butane (putrescine).Also can use triethylene glycol diamine.In one embodiment, polyamines exists with the concentration of the 3-15wt% of reaction mixture.Depend on required physicals and set time, can use other concentration.

Can use can with the crosslinked any suitable polyacrylic ester of carbon-carbon double bond.The example of suitable polyacrylic ester is a tetraacrylate, as by Smyrna, and the Ebecryl  140 that the UBC Chemicals Corp. of GA sells.

Epoxy curing agent

Can use any suitable epoxy curing agent.Example comprises polyamines, poly carboxylic acid, mercaptan (preferably having two or more thiol groups), phenols (less preferred again have two or more phenolic group) or the like.The example of suitable stiffening agent comprises alicyclic diamine, as isophorone diamine, 1, and 2-diamino-cyclohexane, double mutual-amido cyclohexyl methane and 1,3-BAC (two amino methyl hexanaphthene) hyperergy alicyclic diamine, or the mixture of diethylenetriamine.Stiffening agent typically exists with the concentration of the 3-15wt% of epoxy curing agent.

The free radical catalyst of thermal activation

Can use the free radical catalyst of any thermal activation of the crosslinked olefin group that in Viscotrol C or ricinolic acid (and/or material of other olefine-containing group), exists of energy.This catalyzer is that skilled those skilled in the art is known, with comprise for example one or more (1) 2,5-2, (2) 1,4-two-(2-t-butylperoxy sec.-propyl) benzene, tert-butyl peroxide cumyl, (3) di-t-butyl peroxide, (4) 2,4,4-tri-methyl-amyl-2-hydroperoxide, (5) diisopropyl benzene list hydroperoxide, (6) cumene hydroperoxide and (7) Diisopropyl azodicarboxylate (AIBN).In one embodiment, 2 of its commodity Triganox 101-45B by name, 5-2 superoxide is a catalyzer.

Can advantageously at room temperature activate superoxide, for example methylethylketone (MEK) superoxide as radical polymerization initiator.Other superoxide such as di-t-butyl peroxide, dibenzoyl peroxide, dicumyl peroxide etc. can at high temperature be used for solidifying.In one embodiment, based on composition weight, use the content of about 0.1-about 5%.In another embodiment, also can use and under 25 ℃, demonstrated 10 hours or other superoxide of transformation period still less.In yet another embodiment, use the mixture of superoxide with different activation temperatures.

Filler

Can use any filler that is used in combination with polymer materials, for example those that in the industry of floor, use.Advantageously after forming polylactone, add filler, but can when the PPN structure forms, exist.No matter the polylactone prepolymer is direct and second polymer reaction, still no matter the polylactone prepolymer reacts with part that contains epoxy group(ing) and poly carboxylic acid, at this produce in situ second polymer material, this all is facts.

Can use and brighten filler increase opaqueness.The optical property of titanium dioxide makes it to become good especially pigment and comes to such an extent that have the white of good opaqueness.If in this layer, use white filler such as lime carbonate, then can use the titanium dioxide of lower aq with moderate content.

Lime carbonate is particularly useful.Hardness, rigidity, thermal migration temperature, sliding resistance, anti-stress crack, weldability, impressionability and resistance to blocking all are improved.The perviousness of percent thermal shrinkage and elongation and water vapour and oxygen descends.

Talcum is another filler that is suitable for very much the reinforcement polymer materials that uses in floor coating.Opposite with the granular texture of the lime carbonate of low length-to-diameter ratio, it has laminate structure.Just increase rigidity, thermal migration temperature and dimensional stability, this stratiform form makes talcum more effective than lime carbonate.With respect to lime carbonate, the steatitic shortcoming concentrates on shock strength, mat surface and the lower thermo-oxidative stability of reduction.Mica also has laminate structure and has confers similar advantages and shortcoming.

On the Young's modulus, tensile strength and the heat-drawn wire that increase elastomer material described herein, the filler/strongthener of high length-diameter ratio such as wollastonite and glass fibre are than talcum with mica can have even stronger effect.

The improvement that inorganic additives by high length-diameter ratio provides can be assisted especially and be used permanent softening agent or processing aid, these ground coating systems of making as the liquid paraffins.In these cases, the rigidity effect of this additive can compensate the loss of rigidity that the liquid paraffins produces.

In the important elastomer material of antiseized therein and impressionability, the system of forging of low levels (0.1-1.5%) or the silicon oxide of precipitation forms are useful.In the floor coating system, these will be that wearing layer and printed design apply layer thereon.

For most of systems, the reinforcement that diameter can provide the same type performance that is provided by lime carbonate less than the hibbsite and the magnesium hydroxide of 40 microns appropriate granularity.In addition, they can provide the fire prevention and the smog controlling features of usefulness.

Can strengthen polymer materials by using the light and heat stablizer, when it uses in the coating system of ground.For thermo-stabilizer, consumption that should use and type will change with making the employed practical methods of final structure.Melt spreading device method can provide the product that has than melt rolls or extrusion molding route thermal history is lacked.Yet, in some cases, in this technological process, can expose polymer materials in the following for some time of temperature that surpasses 200 ℃.

Suitable stabilizers comprises randomly having co-stabilizer such as organosulfur compound, for example the hindered phenol of thio-2 acid 2 stearyl ester (DSTDP).Use the high-molecular weight hindered phenol, as Irganox 1010 available from Ciba-Geigy, and one or more secondary oxidation inhibitor such as thioether and phosphorus compound, can obtain good thermostability.DSTDP and Ultranox 626 available from GE are examples of this class material.Effective thermo-stabilizer bag from this system is 0.1%Irganox1010,0.1%DSTDP and 0.05%Ultranox 626.

Hindered amine as light stabilizer (HALS) avoids especially effective aspect the photoxidation at the protection polymkeric substance.Polymkeric substance HALS, as the Luchem HA-B18 available from Atochem, itself is effective especially and have additional advantage, does not promptly demonstrate the antagonism of other additive such as DSTDP.Externally comprise in the wearing layer in 0.3%Luchem HA-B18 and the layer below this transparent wearing layer and comprise that 0.15% will improve the photostabilization of floor coating widely.

Can make with lubricator and make the floor with processing aid.This depends on specific technology fully.For extrusion molding or melt calendering operation, external lubricant can have booster action.Calcium stearate and Zinic stearas are suitable for as external lubricant.They also can provide some extra stable carrier.Optionally, with 0.1-1.0%, the scope of preferred 0.2-1.0% is added them.

Can in polymer materials, use the processing aid adjusting or strengthen specific machining feature as the energy requirement of reduction and/or the process velocity of increase.

The combustibility of ground finishing coat and the smog that can use various additive improved polymer materialss, polymer sheet and contain this polymer sheet generate.At high temperature discharge the various mineral compound of water outlet, be used as binary filler/fire retardant as hibbsite and magnesium hydroxide.Aspect the combustion characteristic that improves polylactic acid based system, phosphorus compound, borate and zinc oxide all can play useful effect.

Other additive that can be included in the polymer materials comprises dyestuff, printing ink, oxidation inhibitor etc., uses these with the relatively little content less than 50PHR usually.

Antistatic feature also can be important for some are used.Many anti static additives are to have hydrophilic and compound hydrophobic part.This class commercial materials is to have longer chain fatty acid, as stearic polyvalent alcohol, as the monoesters of glycerine.

Also can add rosin.

II.PPN is synthetic

Advantageously be equipped with the PPN structure with the two-stage cure legal system.First step in curing process is included under the inert nitrogen covering, and heating contains two kinds of prepolymers or polylactone and contains the molecule and the polycarboxylic composition of epoxy group(ing), up to forming gel liquid.Then can be in parallel pressing plate mould or in forming mould, this gel of Procuring under pressure.

The Procuring Viscotrol C forms intermediate polyester (polylactone) material, and crosslinked afterwards this intermediate forms interpenetrating(polymer)networks and has several advantages.At high temperature forming the polyester key is to form the condensation reaction of water as by product.Water can leave the hole in the gelationization structure and must remove any hole to keep the structural integrity of the finished product.Under pressure, carry out pre-cure step and minimize hole formation.In addition, step reaction forms interpenetrating polymer networks (PPN), for example reacts control method when being between ESO and sebacic acid.Last reaction can require for some time, and this system reaches gelation point afterwards.Only after reaching gelation point, said composition just has competent viscosity, when applying slight pressure, prevents the open mould of its outflow.

Polylactone can with the material that contains epoxy group(ing), as the reaction of Resins, epoxy and/or epoxidized vegetable oil, under relatively-high temperature and crosslinked under the pressure of 1-3atm, form elastomer material then.Can react as polyamines, poly carboxylic acid, mercaptan and phenols with stiffening agent (epoxy hardener) by the epoxy group(ing) that side is hung, take place crosslinkedly, this is well known in the art.If there is the radical initiator (crosslinking catalyst) of thermal activation, its also two key in the ricinolic acid part in the crosslinkable polymer main chain then.In one embodiment, have the linking agent contain alkene, as Vinylstyrene and other diolefine and/or polyene hydrocarbon to provide further crosslinked.

Can use the two-stage cure method, the synthetic elastomer material.The first step in curing process comprises that in the presence of the catalysts for radical polymerization of acid catalyst and/or thermal activation, under inert nitrogen covered, heating contained the composition of Viscotrol C (or ricinolic acid), up to forming gel thick liquid or semisolid.Can in final step, under pressure, for example in parallel pressing plate mould, solidify this material then.

Polylactone typically exists with about 20 to about 80wt% the consumption between reaction mixture.The material that contains epoxy group(ing) typically exists with about 20 to about 80wt% the consumption between reaction mixture.Stiffening agent or linking agent typically exist with about 2 to about 20wt% the consumption between reaction mixture.Crosslinking catalyst typically exists with about 0.1 to about 5wt% the consumption between reaction mixture.

Typically, the Procuring time range can be about 60 minutes of about 20-, but this can regulate according to composition and catalyzer.In one embodiment, the Procuring time is about 30 minutes.In addition, the present invention has instructed can be by being linked on the ESO structure that polyamines causes, thereby generate network structure, meanwhile, can form other crosslinking structure by the unsaturated double-bond of radical crosslinking in the Viscotrol C polylactone of peroxide-induced.In addition, if use polyamines stiffening agent or linking agent, then carboxyl-amine reaction is possible between sour site and polyamines.The structure that this back one reaction promotes extra interface stability and becomes final elastomer product.In one embodiment, can use one or more polyamines.In another embodiment, polyamines can be an alicyclic diamine, as (1) isophorone diamine, (2) 1, the 2-diamino-cyclohexane, (3) biconjugate amido cyclohexyl-methane and 1,3-BAC hyperergy alicyclic diamine, (4) triethylene glycol diamine, (5) 1,5-diamino pentanes (cadaverine) and (6) 1,4-diaminobutanes (putrescine).In another embodiment, use triethylene glycol diamine.In one embodiment, for the polyamines linking agent, use the concentration of the about 15wt% of about 3-.Depend on required physicals and set time, can use other concentration.The Procuring temperature range of polyamines typically is about 220 ℃ of about 140-, but can use the temperature beyond this scope.In one embodiment, use about 200 ℃-Yue 205 ℃ Procuring temperature.

Can be by changing (from above those that describe independently) the ricinolic acid prepolymer in reaction vessel, exist, epoxidized vegetable oil such as ESO, linking agent, crosslinking catalyst, as the relative quantity of MEK superoxide or benzoyl peroxide, change the various physical and mechanical properties of elastomer material.Can be by using epoxidized vegetable oil, as ESO, rather than petroleum base Resins, epoxy, increase " natural " content of polymer materials.

In one embodiment, be under the room temperature generation solidified situation that reaction mixture comprises etc. that the ricinolic acid of weight consumption or the mixture of Viscotrol C polylactone, Resins, epoxy and two amine crosslinkers add the 0.1%MEK superoxide.These compositions are joined in the reaction vessel, and fully stir, to guarantee the uniform mixing of each composition.Then, after because of exothermic polymerization reaction rising starting temperature, followed by under successive stirs, (typically 0 of polymeric constituent to about 80wt% with the filler of aequum, more typically about 40 to about 60wt%) join in this mixture, up to forming gel or thick liquid.Can between the parallel plate of water pressure engine, place a part of this thick liquid and at room temperature, solidify about 12 hours of this sample down or spend the night at slightly high pressure (typically between about 1 to about 3atm).The sample of compacting can be under about 60 ℃ panel temperature about 4 hours of after fixing, relief pressure on mould afterwards.May importantly fully cool off, for example after about 30 minutes, just discharge die pressure up to press and sample.For example by about 2 hours of about 80 ℃ of following after fixing, sample can solidify more quickly.

In another example, but use also outer time of savings of thermofixation.Use this method, with ricinolic acid polylactone and Resins, epoxy, with epoxidized vegetable oil, be placed in the reaction vessel as the mixture of ESO, and violent stirring at ambient temperature.Then, with the filler of aequum, two amine crosslinkers of about 10wt% and the benzoyl peroxide of about 2wt% all join in this mixture, stir this mixture, up to forming gel or thick liquid.The same the same, thick liquid can be under slightly high pressure, but solidified about 4 hours down at about 120 ℃, then about 4 hours of about 60 ℃ of following after fixing.Be cooled to 10 ℃ room temperature just advantageously to discharge platen pressure after interior up to mould once more.Although do not wish to be bound by specific theory, but think in curing process, that is to say, when water discharges as by product and before material is had an opportunity abundant oxidation, keep this pressure and cooled off the shape that to keep polymer materials up to reaction vessel.

As typical synthetic example, with aequum as above described independently castor oil soap, epoxidized soybean oil and sebacic acid are incorporated in the reaction vessel.Make this mixture be elevated to 142 ℃, and under violent stirring, kept about 30 minutes, perhaps up to obtaining amber solution.With about 5 minutes, the superoxide that adds required amount added the limestone filler of pulverizing afterwards in red-hot mixture under continuously stirring.Then this mixture is transferred in the culture dish, and under nitrogen covers, be heated to 200 ℃, up to obtaining the fixed structure through 30 minutes.Then this soft solid materials is placed in the rectangular sheet mould, is placed on this rectangular sheet mould in the parallel platen press and solidified about 4 hours.In this synthetic method, the instruction parent material is to have about 90% ricinolic acid of about 80%-and the range of viscosities under 25 ℃ is the Viscotrol C of 63-69 centipoise.In this example, epoxidized soybean oil is a vegetables oil, but also can use other epoxidized vegetable oil, as acroleic acid esterification epoxidized soybean oil (AESO), maleinization soya-bean oil direactive glyceride (SOMG/MA) or epoxidized soybean oil fatty acid methyl ester (MESO).

In one embodiment, can use one or more peroxide activators, as (1) 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, (2) 1,4-two-(2-t-butylperoxy sec.-propyl) benzene, tert-butyl peroxide cumyl, (3) di-t-butyl peroxide, (4) 2,4,4-tri-methyl-amyl-2-hydroperoxide, (5) diisopropyl benzene list hydroperoxide, or (6) cumene hydroperoxide.In another embodiment, 2 of its commodity Triganox 101-45B by name, 5-2 superoxide is a catalyzer.The selection of the binding substances of superoxide or superoxide be not limited to above-mentioned these, can select superoxide to adapt to required technology.Typically, the Procuring time range can be about 60 minutes of about 20-, but this can regulate according to composition and catalyzer.In one embodiment, the Procuring time is about 30 minutes.

Can cause being linked on the epoxidation structure by polyamines, meanwhile (for example, by the unsaturated double-bond in the radical crosslinking Viscotrol C polylactone of peroxide-induced) forms other crosslinked structure, thereby generates the interpenetrating polymer networks structure.In addition, if use the polyamines linking agent, then carboxyl-amine reaction is possible between sour site and polyamines.The structure that this back one reaction promotes extra interface stability and becomes final elastomer product.In one embodiment, can use one or more polyamines.When using polyamines, the Procuring temperature range typically is about 220 ℃ of about 140-, but can use the temperature beyond this scope.In one embodiment, use about 200 ℃-Yue 205 ℃ Procuring temperature.

The scale that depends on polyreaction is thought the heat-transfer capability that can change heat release degree and reaction vessel.In some embodiments, can advantageously comprise one or more inert fillers in reaction mixture, they can serve as the heat release of radiator element subcontrol polyreaction at this.

III. the sheet material that comprises this polymer materials

Can use this elastomer material to prepare top coat and/or surface component, as ground and wall coating prod by reproducible natural matter with good mechanical properties.Except other required shape, elastomer material can form sheet material.Can prepare sheet material by following step:

A) provide suitable prepolymer, the compound that contains epoxy group(ing) and epoxy crosslinking agent (comprising poly carboxylic acid), randomly one or more crosslinking catalysts and at least a additive that contains filler,

B) typically be coated with by the shop or roll with this material form sheet-form and

C) be heated to suitable processing temperature and mix and

D) randomly if necessary in finishing embossed sheet before the final curing, thus the cooling resulting sheet.

Can use various known processing units heating and thoroughly mix each material.These include, but not limited to Banbury, shredder and kneader.In one embodiment, closely mix the suitable time period of each component (up to each material by thorough mixing) in high shear mixer, making is not having under the situation of remarkable degradation of mixture, and this mixture becomes fluid state on substantially.

IV. mix the flooring material of polymer materials

Can use the sheet material that forms by elastomer material as being coated with based on the routine shop or rolling in the floor coating of technology one or more layers.Floor coating comprises the sheet material of the described from here polymer materials formation of one deck at least.In general, form uniform floor sheet material by the infill system that includes about 10%-90wt% filler at polymeric matrix.Perhaps, can prepare floor heterogeneous sheet material, have the two-layer of specific function or a multilayer different layers comprising what bond together.For example, floor coating typically comprises provides the buffered foaming layer; Substrate, the solid undercoat; Wearing layer and/or finishing coat.Also can use carrier or substrate as weaving or nonwoven web or fabric thin paper and glass web and fiber.

Elastomer material described herein can be used for forming stratum basale, wearing layer and even can use conventional foaming technique foaming, form foaming layer.Can comprise equally various DESIGNED FEATURE and can be ideally in the register with particular design pattern (register) physics and/or mechanically give each lamination flower.Also graph image can be incorporated in the floor, so that the image with depth preception to be provided, as described in the U.S. Patent No. 5347296, its content is introduced by reference in its entirety at this

Foaming

For the application of some types, requiring does not have in the layer of some or all of floor coating structures or seldom foaming.Yet floor coating can change to those of wherein none composition layer foaming from those floor coatings that wherein all layers all foam except finishing coat.Foams can be closed-cell foams.Can make this layer foaming by using chemical foaming agent.Azo-compound is effective especially.The example of this compounds is azodicarboamide (available from Uniroyal Celogen AZ).The useful especially feature of this compound is that by using activator such as zinc oxide, its decomposition point can drop to less than 170 ℃ from 220 ℃.If use the printing ink contain benzotriazole on the surface of foamable substrate or contain printing on the layer of Celogen AZ and zinc oxide, and heat at the resulting structures that adds wearing layer in the foaming layer and arrive between activation and inactivation decomposition temperature, in sample, generate the pattern (chemical embossing) of projection then.Also can use and replenish whipping agent such as hibbsite,, and when being heated to above 200 ℃, discharge water vapour because it not only serves as fire retardant.Fugitive processing aid of volatility or softening agent whipping agent as a supplement also can have useful effect.

Also can use the mechanical foaming technology in conjunction with chemical foaming agent or instead of chemical whipping agent.This typically is included under the condition that will produce required abscess quantity and size in the required foams, mixing air or another gas and polymer materials.Be coated with in the system in the shop, the mixture that is applied need have the foamy structure that approaches desired product.In extrusion molding or calendering process, gas need the solution in polymkeric substance in or in the extruding machine system under melt pressure as little microvesicle.When melt leaves extruding machine and, foams when becoming normal atmosphere from high pressure (the about 700PSI of about 100-).In both cases, importantly drop to fast and be lower than abscess and shrink or be out of shape required temperature, under required size, freeze foam structure by sheet temperature.

With reference to following limiting examples, will understand the present invention better.

Embodiment 1

The Viscotrol C pre-polymerization forms the prepolymer polylactone

With 1: 0.08 ratio (by weight promptly, 8 parts of citric acids are to 100 parts of Viscotrol C) blend Viscotrol C (ricinolic acid) and citric acid.In this solution, add 1.0%p-TSA and 2wt% peroxide catalyst 101-45B-pd.Heat this mixture to 210 ℃ (+or-10 ℃) then, and nitrogen cover and stirring at low speed under, maintenance is 1 hour under this temperature.This method produces the thickness polylactone prepolymer of light color.

Embodiment 2

PPN is synthetic

Prescription: phr

A. the Viscotrol C polylactone prepolymer 100 of embodiment 1

b.ESO 267

C. sebacic acid 133

D.2,5-dimethyl-2,5-two (t-butylperoxy) 5.3

The hexane superoxide

E. Wingdale 500

Operation: in the single neck flask of 500ml, mix 100ml composition (a) with 267g (b) and 133ml (c) and be placed in the temperature control oil bath.Heat this mixture and descend stirring 10 minutes at 142 ℃.Add 5.3g (d) and 500g (e), and this mixture of violent stirring 6 minutes, and make it cool to room temperature.The gained mixture is placed in the culture dish, and under inert gas, was heated to 200 ℃, make it cool to room temperature afterwards once more through 30 minutes.The mixture of this Procuring is transferred to 6 " * 6 " * 1/8 " the teflon mould in and place it in the water pressure engine.The pressure that applies about 5000psi is to pressing plate.Solidified sample is 4 hours under the temperature of this pressure and 195 ℃., turn off well heater and the sample of after fixing was cooled off 30 minutes after the period at this section, discharge platen pressure afterwards and from mould, take out sample.

Embodiment 3

PPN is synthetic

Prescription: phr

A. the Viscotrol C polylactone prepolymer 100 of embodiment 1

b.ESO 267

C. sebacic acid 133

D. Resins, epoxy 17

E.1, the 4-diaminobutane 17

F.2,5-dimethyl-2,5-two (t-butylperoxy) 5.3

The hexane superoxide

G. Wingdale 500

Operation: in the single neck flask of 500ml, mix 100ml composition (a) with 267g (b) and 133ml (c) and be placed in the temperature control oil bath.Heat this mixture and descend stirring 10 minutes at 142 ℃.Add 17g (d), 17g (e), 5.3g (f) and 500g (g), and other 10 minutes of this mixture of violent stirring, and make it cool to room temperature.The gained mixture is placed in the culture dish, and when inert gas covers, through 30 minutes reheat to 200 ℃.According to this operation, with sample transfer to 6 " * 6 " * 1/8 " the teflon mould in and place it in the water pressure engine.The pressure that applies about 5000psi is to pressing plate.Solidified sample is 4 hours under the temperature of this pressure and 195 ℃.After solidifying, at room temperature cooled off sample 30 minutes, and discharge platen pressure and from mould, take out sample sheets.

Embodiment 4

PPN is synthetic

Prescription: phr

A. the Viscotrol C polylactone prepolymer 100 of embodiment 1

B. citric acid 5

c.ESO 265

D. sebacic acid 130

E.2,5-dimethyl-2,5-two (t-butylperoxy) 3

The hexane superoxide

F. Wingdale 500

Operation: in the 500ml beaker, mix each composition (a), (c) of listed consumption and (d).Heat this mixture, and use, stirred 0.5 hour down at 157 ℃ for the inert nitrogen bubbler that stirs.Add component (b), (e) and (f), and other 5 minutes of violent stirring mixture, make this mixture cool to room temperature afterwards.The gained mixture is placed in the culture dish, and under inert nitrogen covers through 30 minutes reheat to 200 ℃, form the mixture of Procuring.Cool off the mixture of Procuring once more, transfer to 6 " * 6 " * 1/8 then " the teflon mould in.This mixture and mould are placed in the water pressure engine, and the pressure that applies about 5000psi is to pressing plate.Solidified sample is 4 hours under the temperature of this pressure and 195 ℃.Before discharging platen pressure and from mould, taking out sample, about 30 minutes of cooling sample.

Embodiment 5

PPN is synthetic

Prescription: phr

A. Viscotrol C 100

B. citric acid 8

c.p-TSA 1

d.ESO 300

E. sebacic acid 150

F.2,5-dimethyl-2,5-two (t-butylperoxy) 3

The hexane superoxide

G. Wingdale 500

Operation: in the 500ml three-necked flask, mix 100ml composition (a) with 10g (b) and 1g (c) and be placed in the temperature control oil bath.Heated this mixture 10 minutes down at 200 ℃, up to forming highly viscous amber color liquid mixture.In second 600ml beaker, mix 300g (d) and 150g (e) and 3g (f).Heated this mixture to 142 ℃ and violent stirring 10 minutes.Initial thickness composition from first beaker is transferred in second beaker, and 142 ℃ of following stir abouts 5 minutes.Add the 500g Wingdale and stirred this mixture about 5 minutes.The gained mixture is transferred in the culture dish, and under inert gas covers, be heated to 200 ℃, obtain the material of Procuring, then cool to room temperature through 30 minutes.With gained Procuring sample transfer to 6 " * 6 " * 1/8 " the teflon mould in and this mould is inserted in the water pressure engine.The pressure that applies about 5000psi is to pressing plate.Solidified sample is 4 hours under the temperature of this pressure and 195 ℃.Before discharging platen pressure and taking out sample, solidified sample was cooled off about 30 minutes.

Embodiment 6

PPN is synthetic

Prescription: phr

A. Viscotrol C 100

B. citric acid 10

c.p-TSA 2

d.ESO 300

E. sebacic acid 150

F. triethylene glycol diamine 10

G.2,5-dimethyl-2,5-two (t-butylperoxy) 3

The hexane superoxide

H. Wingdale 500

Use to prepare this material with embodiment 4 described identical operations, different is, before Procuring technology, p-TSA and 10 parts of triethylene glycol diamine of 2phr is joined in this system.

Embodiment 7

PPN is synthetic

Use to prepare this material with embodiment 4 described identical compositions and operation, different is just before Procuring technology, the Resins, epoxy of 30phr and the triethylene glycol diamine of 40phr to be joined in this mixture.

Embodiment 8

PPN is synthetic

Use to prepare this material with embodiment 5 described identical compositions and operation, different is to use the 3wt% polymerized castor oil that applies with solvent method, the employed Wingdale of surface treatment.

Embodiment 9

PPN is synthetic

Prescription: phr

A. Viscotrol C 100

B. citric acid 10

c.p-TSA 1

d.ESO 300

E. sebacic acid 150

F.2,5-dimethyl-2,5-two (t-butylperoxy) 3

The hexane superoxide

G. dicumyl peroxide 2

H. triethylene glycol diamine 15

I. Resins, epoxy 5

J. Wingdale 500

Operation: in 1 liter of three-necked flask, mix 100ml composition (a) and 10g (b) and 1g (c), and center on temperature control heating pot.Under nitrogen stirs, 200 ℃ of following heated mixt 10 minutes, up to forming highly viscous amber color liquid.Reduce the temperature to 135 ℃ and add 300g (d), 150g (e), 3g (f), 2g (g), 15g (h), 5g (i) and 500g (j).Other 5 minutes of violent stirring mixture is transferred in the culture dish then fast.Flow down through the mixture to 150 ℃ of heating in 30 minutes in this culture dish in inert nitrogen.The mixture of this Procuring is transferred to 6 " * 6 " * 1/8 " the teflon mould in, this mould is inserted in the water pressure engine of parallel pressing plate.The pressure that applies about 5000psi is to pressing plate.Solidified sample is 4 hours under the temperature of this pressure and 195 ℃.Before discharging platen pressure and from mould, taking out the sample of after fixing, solidified sample was cooled off about 30 minutes.

Embodiment 10

Prescription: phr

A. Viscotrol C 100

b.ESO 260

C. sebacic acid 140

D.TGDDM Resins, epoxy 20

E.2,5-dimethyl-2,5-two (t-butylperoxy) 3

The hexane superoxide

F. Wingdale 1300

Operation: in the 1000ml beaker, mix 100ml composition (a) and 260g (b) and 140g (c).Heating this mixture to 155 ℃ under mechanical stirring.Add 20g (d), and this mixture of violent stirring 2 minutes.Add 3g (e), and other 1 minute of this mixture of violent stirring.Add 1300g (f) at last, and other 1 minute of this mixture of violent stirring, transfer in the culture dish fast then.Flow down through the mixture to 150 ℃ of heating in 17 minutes in this culture dish in inert nitrogen.The mixture of this Procuring is transferred to 6 " * 6 " * 1/8 " the teflon mould in, this mould is inserted in the water pressure engine of parallel pressing plate.The pressure that applies about 5000psi is to pressing plate.Solidified sample is 0.5 hour under the temperature of this pressure and 195 ℃.Before discharging platen pressure and from mould, taking out the sample of after fixing, solidified sample was cooled off about 30 minutes.

Embodiment 11

Prescription: phr

A. Viscotrol C 100

b.ESO 260

C. sebacic acid 140

D. tetraacrylate (Ebecryl  140) 20

E.2,5-dimethyl-2,5-two (t-butylperoxy) 3

The hexane superoxide

F. Wingdale 1300

Operation: in the 1000ml beaker, mix 100ml composition (a) and 260g (b) and 140g (c).Heating this mixture to 155 ℃ under mechanical stirring.Add 20g (d), and this mixture of violent stirring 2 minutes.Add 3g (e), and other 1 minute of this mixture of violent stirring.Add 1300g (f) at last, and other 1 minute of this mixture of violent stirring, transfer in the culture dish fast then.Flow down through the mixture to 150 ℃ of heating in 17 minutes in this culture dish in inert nitrogen.The mixture of this Procuring is transferred to 6 " * 6 " * 1/8 " the teflon mould in, this mould is inserted in the water pressure engine of parallel pressing plate.The pressure that applies about 5000psi is to pressing plate.Solidified sample is 0.5 hour under the temperature of this pressure and 195 ℃.Before discharging platen pressure and from mould, taking out the sample of after fixing, solidified sample was cooled off about 30 minutes.

Following table 1 shows the mechanical and physical performance data that obtained by the sample bomb gonosome of producing according to these embodiment.

Table 1. is according to the elastomeric mechanical property general introduction of the sample of the operation preparation of listing among embodiment 2,3, the 5-8,10 and 11

Performance	ASTM	Unit	Embodiment 2	Embodiment 3	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 10	Embodiment 11
											Density	D-792	g/cm 3	1.64	1.54	1.53	1.49	1.39	1.46	2.56	2.50
Tensile strength	D-638	MPa	0.6	14.3	0.62	0.37	0.88	0.70	2.41	1.79
											Tensile modulus	D-638	MPa	2.85	41.5	1.53	1.08	1.94	1.44	5.51	6.20
Elongation at break	D-638	％	21	34.6	47.1	40.3	74.6	61.4	11.0	5.0
											The hardness A type sclerometer model 1600 that relaxes	D-2240		A75, creep 12 after 15 seconds	A75, creep 7 after 15 seconds	A57, creep 15 after 15 seconds	A42, creep 10 after 15 seconds	A54, creep 8 after 15 seconds	A55, creep 12 after 15 seconds	A84, creep 5 after 15 seconds	A80, creep 7 after 15 seconds

Enzyme esterification ricinolic acid forms the polylactone prepolymer

It below is the example of the employed operation of enzyme-catalyzed polymerization technology.Take by weighing ricinolic acid (about 10ml) and be incorporated in the 50ml Erlenmeyer flask, this flask is placed on constant temperature maintains in the 60-70 ℃ of oil bath in the scope.Under violent stirring, reduce system pressure to 20in-Hg, and maintain under this level, reach no bubble state up to solution.Terminate in the vacuum in the Erlenmeyer then, and, 10wt% lipase is joined in this Erlenmeyer flask based on the initial mass of ricinolic acid.Set the temperature regulator to 80 ℃ of oil bath, 80 ℃ is optimum temperature range 70-90 ℃ mid point.Reduce the pressure that stirring velocity arrives 150rpm and applies the 20in-Hg vacuum again.Kept these temperature and pressure conditions 72 hours, the partially polymerized reaction of polylactone takes place to form in this process.Along with periodic adjustment stirring velocity time lapse, the viscosity increase of the solution that causes because of polymerization progressively with compensation.

After 72 hours reaction times, filter this prepolymer polylactone solution, separate and remove the grain pearl of magnesium coating.Use Johnson﹠amp; The commercially available Gauze PadsT of Johnson is as filtration medium.Then in apparatus,Soxhlet's with washing with acetone filtering enzyme grain pearl, and the acetone of evaporation of residual and in 2-8 ℃ refrigerator, store washing and the grain pearl of exsiccant magnesium coating for re-using subsequently.In one embodiment, forming the employed enzyme of polylactone solution is by the hydrolysed fat enzyme B from CandidaAntarctic.In our scheme, this enzyme is fixed on the porous propylene acid ester resin pearl and has the initial specific activity of 7000PLU/g.

Following synthetic embodiment synthesizes exemplifying of elastomer material described herein.

Embodiment 12

Prescription: wt%

A. polylactone (ricinolic acid prepolymer) 29.1

B. Resins, epoxy DEGBA 20.8

C. diethylenetriamine 20.8

D.MEK superoxide 0.2

E. wood powder 29.1

Operation: in container, mix by weight regulation or ricinolic acid polylactone and the Resins, epoxy and the diethylenetriamine stiffening agent of amount in proportion, add the 0.2%MEK superoxide, and violent stirring 10 minutes.The wood powder that with the granularity of aequum is 200 orders (0.074mm) then joins in this mixture, and stirs in addition 10 minutes, up to forming fluid gel.This mixture was solidified 1 hour, is placed on 4 " * 4 " * 1/16 then " teflon T-shape mould in, this mould is inserted in the parallel platen press, and applies the hydraulic pressure of 5000psi.Keep this pressure, under ambient room temperature, solidify this sample and spend the night, or about 12 hours.60 ℃ of following solidified sample 4 hours, discharge die pressure in the cooling of compacting sample after 20 minutes then.

Embodiment 13

Prescription: wt%

A. polylactone (ricinolic acid prepolymer) 24.5

B. Resins, epoxy DEGBA 12

C. diethylenetriamine 13

D. benzoyl peroxide 1

E. Wingdale 49.5

Operation: mix ricinolic acid polylactone and Resins, epoxy and polyamines stiffening agent in container, add 1% benzoyl peroxide, violent stirring is 10 minutes then.Wingdale with institute's required amount joins in this mixture then, and stirs in addition 10 minutes, up to forming gel or thick liquid nano suspension.This mixture was solidified 1 hour, is placed on 4 " * 4 " * 1/16 then " teflon T-shape mould in, this mould is inserted between the pressing plate of water pressure engine, and applies the pressure of 5000psi.Curing mixture 1.5 hours and solidified 3 hours down under 85 ℃ temperature at 120 ℃.

Embodiment 14

Prescription: wt%

Polylactone (ricinolic acid prepolymer) 10.7

Resins, epoxy DEGBA 10.7

Diethylenetriamine 10.7

Epoxidized soybean oil 10.7

MEK superoxide 0.15

Wingdale 54

TiO ₂ 3

Operation: in container, mix ricinolic acid polylactone and Resins, epoxy, polyamines stiffening agent, and epoxidized soybean oil, add the 0.15%MEK superoxide, and violent stirring 10 minutes.The filler of institute's required amount is joined in this mixture, and stirred in addition 10 minutes, up to forming gel suspension.This blend sample is placed on 4 " * 4 " * 1/16 " teflon T-shape mould in, and this mould is inserted into the pressure 12 hours that in the water pressure engine and at room temperature applies 5000psi.

Embodiment 15

Prescription: wt%

A. polylactone (ricinolic acid prepolymer) 16.6

B. Resins, epoxy DEGBA 16.6

C. diethylenetriamine 16.6

D. epoxidized soybean oil 16.6

E.MEK superoxide 0.23

F. wood powder 23.3

g.TiO ₂ 10

Operation: use the same processes described in the embodiment 3, different is with granularity is the alternative fillers of 200 purpose wood powders.

Embodiment 16

Prescription: wt%

A. polylactone (ricinolic acid prepolymer) 10.6

B. Resins, epoxy DEGBA 9.5

C. diethylenetriamine 11.6

D. epoxidized soybean oil 10.6

E. benzoyl peroxide 0.4

F. triethylene glycol diamine 0.4

G. Wingdale 53

Operation: the ricinolic acid polylactone and Resins, epoxy and the epoxidized soybean oil that in the 100ml beaker, mix aequum by weight.And this mixture of violent stirring, and 11.6% polyamines and 0.4% triethylene glycol diamine stiffening agent and 0.4% benzoyl peroxide joined in this container, and stirred in addition 5 minutes.Limestone filler is incorporated in this mixture, and stirred in addition 10 minutes, up to forming gel or thick liquid.This mixture was solidified 1 hour, is placed on 4 " * 4 " * 1/16 then " teflon T-shape mould in, this mould is inserted in the thermocompressor, and under 90 ℃ constant temperature, applies the hydraulic fluid pressure 2 hours of 5000psi.

Embodiment 17

Prescription: wt%

A. polylactone (ricinolic acid prepolymer) 7.6

B. Resins, epoxy DEGBA 10.6

C. diethylenetriamine 11

D. epoxidized soybean oil 7.6

E. triethylene glycol diamine 2.3

f.MEK 0.4

G. Wingdale 61

Operation: in container, mix ricinolic acid polylactone and Resins, epoxy and petroleum base polyamines stiffening agent, epoxidized soybean oil, triethylene glycol diamine and the MEK superoxide of aequum by weight, and violent stirring 10 minutes.Limestone filler is incorporated in this mixture, and stirred in addition 10 minutes, up to forming gel or thick liquid nano suspension.This mixture is independently being solidified in the container, and under nitrogen covers, be heated to 180 ℃, up to forming the fixed semisolid through 1 hour.The mixture of this Procuring is transferred to 4 " * 4 " * 1/16 " teflon T-shape mould in, this mould is inserted in the thermocompressor, and under 180 ℃ constant temperature, applies the hydraulic fluid pressure 4 hours of 5000psi.

Table 2 has been listed the sheet material of producing by the operation described in aforementioned 6 each embodiment, therefrom the physical performance data of the laboratory sample of cutting acquisition.

Elastomeric physicals general introduction among the table 2. embodiment 12-17

	ASTM	Unit	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16	Embodiment 17
									Density	D-792	g/cm 3	0.99	1.66	1.57	1.14	1.57	1.67
Tensile strength	D-638	MPa	2.67	0.40	0.30	1.64	0.58	1.09
									Tensile modulus	D-638	MPa	2.98	0.47	0.75	2.94	3.22	4.22
Elongation at break	D-638	％	94.9	180.0	136.5	55.8	24.6	262.5
									The hardness A type sclerometer model 1600 that relaxes	ASTM D-2240		A66, creep 15 in the time of 12 seconds	A57, creep 14 in the time of 15 seconds	A60, creep 7 in the time of 15 seconds	A76, creep 13 in the time of 15 seconds	A53, creep 14 in the time of 15 seconds	A80, creep 26 in the time of 15 seconds

Table 1 and 2 data show, elastic composition has and is suitable for use as flooring product with sheet material or be entrained in flooring product with the performance in the sheet material.

The performance that can provide curing composition to use in floor coating is provided the composition that has following ranges component by weight based on the gross weight of composition: the ricinolic acid polylactone of the about 15wt% of about 5%-, the crosslinking catalyst of the about 0.4wt% of about 0.05%-(in one embodiment, be the about 0.2wt% methyl ethyl ketone peroxide of 0.05%-, in another embodiment, benzoyl peroxide for the about 4wt% of about 0.05%-), the compound that contains epoxy group(ing) of about 5%-30wt%, the about 15wt% epoxy curing agent of about 5%-, the about 80wt% filler of about 3%-(in one embodiment, be the about 80wt% of about 18%-, in another embodiment, wood powder for the about 33wt% of about 3%-), about 30wt% epoxidized soybean oil of about 5%-and the about 30wt% Resins, epoxy of about 5%-.

Although disclosed theme of the present invention, should it is evident that in view of the present invention, many modifications of the present invention, to substitute and change be possible.Be appreciated that and beyond describing particularly, put into practice the present invention.This modification, substitute and change and intend being included in the application's the scope.

Claims (22)

1. composition, it comprises:

A) be selected from Viscotrol C, ricinolic acid, Viscotrol C polylactone, ricinolic acid polylactone and in conjunction with in the ricinolic acid component, preferred ricinolic acid polylactone, more preferably by the polylactone of enzyme-catalyzed polymerization preparation and wherein enzyme preferably be derived from the lipase of Candida Antarctica

B) be selected from Resins, epoxy, epoxidized vegetable oil and in conjunction with in the compound that contains epoxy group(ing), diglycidylether, epoxidized soybean oil and the combination thereof of preferred four glycidyl group diaminodiphenyl-methane, dihydroxyphenyl propane,

C) linking agent, preferred polyfunctional amine, poly carboxylic acid, polyacrylic ester or its combination, the wherein preferred sebacic acid of poly carboxylic acid, citric acid or its combination, with the preferred isophorone diamine of polyfunctional amine, 1,2-diamino-cyclohexane, double mutual-amido cyclohexyl methane, 1,3-BAC hyperergy alicyclic diamine, diethylenetriamine, 4,4 '-isopropylidene diamines, 1,4-diaminobutane, triethylene glycol diamine or its combination and

D) randomly be selected from crosslinking catalyst, filler and in conjunction with in additional component, the wherein preferred wood powder of the radical initiator of the preferred thermal activation of crosslinking catalyst and filler, Wingdale, titanium dioxide, kaolin clay and combination thereof.

2. the composition of claim 1, wherein linking agent is that poly carboxylic acid and said composition further comprise polyamines.

3. top coat, it comprises and contains at least a component that right requires 1 composition.

4. the top coat of claim 3, wherein this top coat is a floor coating.

5. composition, it comprises the reaction product of the composition of claim 1.

6. floor coating, it comprises and contains at least a component that right requires 5 composition.

7. composition, it comprises the reaction product that contains following composition:

(a) reaction product of the composition of claim 1, wherein linking agent is sebacic acid, citric acid or its combination,

(b) crosslinking catalyst is 2,5-2 superoxide and

(c) randomly, triethylene glycol diamine, efflorescence Wingdale or its combination.

8. composition, it comprises:

A) reaction product of poly carboxylic acid and epoxidized vegetable oil,

B) be selected from Viscotrol C, ricinolic acid, Viscotrol C polylactone, ricinolic acid polylactone and in conjunction with in component, with polycarboxylic reaction product and

C) the randomly radical initiator of thermal activation, filler or its combination.

9. interpenetrating polymer networks, it comprises:

A) contain the polyester backbone of esterification ricinolic acid, wherein

I) this polyester backbone comprise be selected from hydroxylic moiety, carboxylic moiety and in conjunction with in side hang part and

Ii) the side on polyester backbone is hung the hydroxylic moiety covalency and is coupled to and contains the containing on the epoxy group(ing) in the epoxy compounds of at least two epoxy group(ing),

B) with the epoxy curing agent that contains at least two epoxy group(ing) covalent cross-linkings in the epoxy compounds that is covalently bound on the polyester backbone, wherein this epoxy curing agent is selected from diamines, polyamines, dicarboxylic acid, poly carboxylic acid, mercaptan and phenols, wherein contain diglycidylether, epoxidized soybean oil or its combination of the preferred dihydroxyphenyl propane of compound of epoxy group(ing)

C) randomly, generate the crosslinking catalyst of free radical, preferred methyl ethyl ketone peroxide, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide or its combination and

D) randomly, filler, preferred wood powder, Wingdale, titanium dioxide, kaolin clay or its combination.

10. combination with decorative surfaces coating, it comprises and contains at least a component that right requires 9 interpenetrating polymer networks.

11. the combination with decorative surfaces coating of claim 10, wherein top coat is a floor coating.

12. an elastomer polymer sheet material, it comprises the interpenetrating polymer networks of claim 9.

13. a method of weaving ricinolic acid or ricinolic acid polylactone based polyalcohol, this method comprises:

(a) mixing and heating

(i) be selected from Viscotrol C, Viscotrol C polylactone, ricinolic acid, ricinolic acid polylactone and in conjunction with in the ricinolic acid component, preferred ricinolic acid polylactone,

(ii) linking agent, preferred poly carboxylic acid,

(iii) be selected from the compound that contains epoxy group(ing) in Resins, epoxy, epoxidized vegetable oil and the combination thereof, preferred epoxidized soybean oil,

(iv) randomly, crosslinking catalyst, the radical initiator of preferred thermal activation and

(v) randomly, filler,

With the material that forms Procuring and

(b) preferably under pressure, at material between about 180 ℃ of these Procuring of heating to about 220 ℃ temperature.

14. the method for claim 13, wherein add crosslinking catalyst and randomly filler to ricinolic acid component, linking agent with before containing in the mixture of compound of epoxy group(ing), mix and heating ricinolic acid component, linking agent and contain the compound of epoxy group(ing), and heating contains the mixture of crosslinking catalyst, the material of formation Procuring.

15. the method for claim 13, wherein crosslinking catalyst is that benzoyl peroxide and the material that heats this Procuring arrive between about 85 ℃-Yue 125 ℃ temperature.

16. the method for claim 13, wherein linking agent is that poly carboxylic acid and step (a) comprising:

(i) in the presence of acid catalyst, make to contain ricinolic acid component and poly carboxylic acid, the composition react of preferred sebacic acid, citric acid or its bonded mixture, wherein the ricinolic acid component is Viscotrol C, ricinolic acid or its combination,

(ii) add second poly carboxylic acid, preferred sebacic acid, citric acid or its combination and epoxidized vegetable oil arrive in the reacted composition of step (i),

(iii) heating steps mixture (ii),

The radical initiator that (iv) adds thermal activation to step (iii) in the mixture of heating and

(v) randomly, add filler in (iv) in step.

17. the method for claim 16, wherein step (ii) in, polyamines is joined in the response composite of step (i), perhaps step (iv) in, polyamines is joined in the mixture of step heating (iii).

18. the method for claim 13, wherein linking agent is that poly carboxylic acid and step (a) comprising:

(i) mix ricinolic acid component and poly carboxylic acid,

The (ii) mixture of heating steps (i),

The radical initiator that (iii) adds epoxidized vegetable oil and thermal activation in the mixture of step heating (ii) and

The (iv) mixture of the heating steps radical initiator that contains epoxidized vegetable oil and thermal activation (iii) forms the material of Procuring.

19. the method for claim 13, wherein linking agent is that poly carboxylic acid and step (a) comprising:

(i) mix ricinolic acid component and poly carboxylic acid and epoxidized vegetable oil,

The (ii) mixture of heating steps (i),

(iii) add crosslinking catalyst and/or filler in the mixture of step heating (ii) and

(iv) heating steps mixture (iii) forms the material of Procuring.

20. the method for claim 13 further is included in before the curing, and this mixture is formed required net shape.

21. the method for claim 13 further comprises partly solidified this mixture, adds filler in this partly solidified mixture, solidifies the mixture that contains filler then.

22. the method for claim 13, wherein by enzyme catalyst, preferably the lipase that obtains from CandidaAntarctic B makes ricinolic acid polylactone prepolymer partially polymerized, makes it afterwards to mix with other component in this mixture.