CN104321377A

CN104321377A - Urea compounds for improving the solid state properties of polyamide resins

Info

Publication number: CN104321377A
Application number: CN201380026163.0A
Authority: CN
Inventors: C·盖布瑞尔; 汉斯-瓦纳·施密特; F·里奇特; 朴惠真; R·夏尔特
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2012-03-20
Filing date: 2013-03-19
Publication date: 2015-01-28
Also published as: WO2013139800A3; JP2015516996A; WO2013139800A2; KR20140144704A; EP2828330A2

Abstract

The present invention relates to the use of at least one urea compound of the formula (I), wherexis 1, 2 or 3; R1 and R2 are selected from hydrogen, linear C1-C7-alkyl, branched C3-C10-alkyl, unsubstituted or substituted C3-C12-cycloalkyl, unsubstituted or substituted C3-C12-cycloalkyl-C1-C4-alkyl, unsubstituted or substituted aryl and unsubstituted or substituted aryl-C1-C4-alkyl; and Z is selected from C3-C10-alkanediyl, unsubstituted or substituted arylene, unsubstitutedor substituted arylene-C1-C4-alkylene-arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted heteroarylene-C1-C4-alkylene-heteroarylene, unsubstituted or substituted C5-C8-cycloalkylene, unsubstituted or substituted C5-C8-cycloalkylene-C1-C4-alkylene-C5-C8-cycloalkylene, unsubstituted or substituted heterocycloalkylene and unsubstituted or substituted heterocycloalkylene-C1-C4-alkylene-heterocycloalkylene for improving at least one solid state property of a polyamide resin. The solid state property is preferably selected from mechanical properties and gloss.

Description

For improvement of the carbamide compound of polyamide resin solid-state properties

The present invention relates to the purposes of a kind of carbamide compound for improvement of polyamide resin solid-state properties.More specifically, the present invention relates to the purposes of a kind of carbamide compound for improvement of polyamide resin mechanical characteristics and gloss.

Polymeric amide (PA) is a kind of well-known commercial polymer, the performance very good due to it and low cost and for much different application, as automobile, aircraft, mechanical engineering, electrically, electronics, motion and leisure industry.Usually attempt to improve polyamide resin be in order to give by they or comprise them the goods of composition molding with favourable characteristic, described characteristic comprises mechanical characteristics, as strengthen Young's modulus, tensile stress at break, break-draw strain or notched Izod impact toughness and outward appearance be as the surface gloss improved.Especially, preferably polyamide resin at high temperature, as second-order transition temperature T _gon, there is good mechanical characteristics.These polymeric amide can be used to manufacture the mechanically stressed parts at high temperature used.Manufacture for thin wall component also requires the good rigidity/toughness of polyamide resin.

As everyone knows, talcum is introduced into the rigidity that can improve polyamide resin in polyamide resin and flexural strength.But this can cause tensile properties and impelling strength to reduce.

JP 5320501 describes containing polyamide resin, as the barium stearate of releasing agent and formula (R ¹nHC (O) NH) ₂the Amilan polyamide resin composition of the double urea compound of X, wherein x is bivalent hydrocarbon radical and R ¹be the aliphatic hydrocarbon group with 9-40 carbon atom, described composition has the mobility of raising, crystallinity and release property.Barium stearate and double urea compound combine give can the polyamide resin of injection moulding with high resistance to extrusion deformation.

Therefore, constantly need the polyamide resin of the solid-state properties with improvement to widen performance spectrum.Described solid-state properties comprises mechanical characteristics and gloss characteristic as surface luster characteristic.Especially, pole needs the polyamide resin demonstrating good mechanical characteristics.

Now have been surprisingly found that the carbamide compound of formula I as described below is suitable for improving the solid-state properties of polyamide resin.

Therefore, the present invention relates to the purposes of the carbamide compound of at least one formula I

Wherein

X is 1,2 or 3;

R ¹and R ²be independently from each other hydrogen, straight chain C ₁-C ₇-alkyl, side chain C ₃-C ₁₀-alkyl, the unsubstituted or C that is substituted ₃-C ₁₂-cycloalkyl, the unsubstituted or C that is substituted ₃-C ₁₂-cycloalkyl-C ₁-C ₄-alkyl, the unsubstituted or aryl that is substituted and aryl-C that is unsubstituted or that be substituted ₁-C ₄-alkyl; And

Z is selected from C ₃-C ₁₀-alkane two base, unsubstituted or the arylidene be substituted, the unsubstituted or arylidene-C that is substituted ₁-C ₄-alkylene-arylene, unsubstituted or the inferior heteroaryl be substituted, the unsubstituted or inferior heteroaryl-C that is substituted ₁-C ₄-alkylidene group-inferior heteroaryl, the unsubstituted or C that is substituted ₅-C ₈-cycloalkylidene, the unsubstituted or C that is substituted ₅-C ₈-cycloalkylidene-C ₁-C ₄-alkylidene group-C ₅-C ₈-cycloalkylidene, the unsubstituted or sub-Heterocyclylalkyl that is substituted and sub-Heterocyclylalkyl-C that is unsubstituted or that be substituted ₁-C ₄-alkylidene group-Ya Heterocyclylalkyl,

Described purposes is the solid-state properties for improvement of polyamide resin.Especially, described solid-state properties is selected from mechanical characteristics and gloss.

The present invention also provides a kind of method improving polyamide resin solid-state material characteristic, and described method comprises and being added in polyamide resin by the carbamide compound of formula I described above at least one.

Term " solid-state properties of polyamide resin " is in the present invention interpreted as the characteristic of polymeric amide in the solid state.Solid-state properties is preferably selected from gloss and mechanical characteristics.Mechanical characteristics comprises such as shearing modulus and tensile properties as the Young's modulus under yielding stress, yield strain, elongation at break, tensile stress at break, tension load and notched Izod impact toughness.

When with do not carry out described add contrast time, the purposes of the carbamide compound of formula I has the following advantage of at least one:

-improve at least one mechanical characteristics, especially, notched Izod impact toughness, elongation at break, tensile stress at break, Young's modulus (Young's modulus) and shearing modulus;

-enhance gloss.

Term " miocrystalline " used herein describes a kind of polyamide polymer having the spike of crystallizing field and the scattering peak of non-crystalline region in X-ray diagram.

For the purpose of the present invention, with being referred to as the variable shown in definition, these be referred to as represent described general in representational substituting group.Definition C _n-C _mrepresent the quantity that each carbon atom is possible in respective substituting group or substituting group part.

Term " C used herein ₁-C ₄-alkyl " represent the straight or branched alkyl with 1 to 4 carbon atoms.Example is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-and the tertiary butyl.

Term " straight chain C used herein ₁-C ₇-alkyl " represent the straight chained alkyl with 1 to 7 carbon atoms.Example is methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl and n-heptyl.

Term " side chain C used herein ₃-C ₁₀-alkyl " represent the branched-chain alkyl with 3 to 10 carbon atoms.Example is sec.-propyl, 2-butyl, isobutyl-, the tertiary butyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 2,2-dimethyl propyl, 1-ethyl propyl, 1,1-dimethyl propyl, 1,2-dimethyl propyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-butyl, 2-ethyl-butyl, 1,1,2-thmethylpropyl, 1,2,2-thmethylpropyl, 1-ethyl-1-methyl-propyl, 1-Ethyl-2-Methyl propyl group, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethyl pentyl group, 2-ethyl pentyl group, 3-ethyl pentyl group, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 1-propylpentyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 1-Methyl Octyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1,2-dimethylhexanyl, 1-propylpentyl, 2-propylpentyl etc.

Term " C used herein ₁-C ₁₀-alkyl " represent the straight or branched alkyl with 1 to 10 carbon atoms.C ₁-C ₁₀the example of-alkyl is for removing C ₁-C ₄-alkyl and side chain C ₃-C ₁₀outside those mentioned by-alkyl, also have n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and positive decyl.

Term " C used herein ₃-C ₁₀-alkane two base " (also referred to as C ₃-C ₁₀-alkylidene group) refer to have the saturated alkyl of the straight or branched of 3-10 carbon atom, one in the hydrogen atom of wherein these groups is replaced by other bonding sites.Straight chain C ₃-C ₆the example of-alkane two base is propane-1,3-bis-base, butane-Isosorbide-5-Nitrae-two base, pentane-1,5-bis-base, hexane-1,6-bis-base.Side chain C ₃-C ₆the example of-alkane two base comprises propyl group-1,1-bis-base, butyl-1,1-bis-base, 1-methyl ethane-1,2-bis-base, 1,2-dimethyl ethane-1,2-bis-base, 1-ethylethanaminium-1,2-bis-base, 1-methylpropane-1,3-bis-base, 2-methylpropane-1,3-bis-base etc.

Term " C used herein ₃-C ₁₂-cycloalkyl " refer to that there are 3 to 12 (=C ₃-C ₁₂-cycloalkyl), normally 5 to 10 carbon atom (=C ₅-C ₁₀-cycloalkyl) monocycle alkyl, bicyclic hydrocarbon base or tricyclic hydrocarbon base.The example with the monocyclic groups of 3 to 10 carbon atoms comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl and ring decyl.The example with the bicyclic groups of 7 to 8 carbon atoms comprises two rings [2,2,1] hexyl, two rings [2,2,1] heptyl, two rings [3,1,1] heptyl, two rings [2,2,2] octyl group and two rings [3,2,1] octyl group.The example of three cyclic groups comprises 1-adamantyl, 2-adamantyl and high adamantyl.C ₃-C ₁₂-cycloalkyl can be unsubstituted or one or more, and such as 1,2 or 3 identical or different radicals R a replaced, and wherein Ra is selected from C ₁-C ₁₀-alkyl or halogen.

Term " C used herein ₅-C ₈-cycloalkylidene " (be also referred to as C ₅-C ₈-cycloalkanes two base) represent above-mentioned cycloalkyl in each case, a hydrogen atom wherein on cycloalkyl ring is replaced by an other binding site, forms divalent moiety thus.C ₅-C ₈-cycloalkylidene can be unsubstituted or one or more, such as 1,2 or 3 identical or different radicals R ^breplace, wherein R ^bbe selected from C ₁-C ₁₀-alkyl or halogen.

Term " C used herein _n-C _m-cycloalkyl-C _o-C _p-alkyl " refer to the above-mentioned cycloalkyl with n to m carbon atom, it is connected to the remainder of molecule by the above-mentioned alkylidene group with o to p carbon atom.Example is cyclopentyl-methyl, cyclopentyl ethyl, cyclopentylpropyi, cyclohexyl methyl, cyclohexyl-ethyl, Cyclohexylpropyl etc.At C _n-C _m-cycloalkyl-C _o-C _pwhen-alkyl is substituted, cycloalkyl moiety has one or more, such as 1,2 or 3 identical or different radicals R ^a, wherein R ^abe selected from C ₁-C ₁₀-alkyl or halogen.

Term " aryl " used herein refers to C ₆-C ₁₄-carbon aromatic group is as phenyl, naphthyl, anthryl and phenanthryl.Aryl can be unsubstituted or one or more, such as 1,2 or 3 identical or different radicals R ^areplaced, wherein R ^abe selected from C ₁-C ₁₀-alkyl or halogen.Preferably, aryl is phenyl.

Term " arylidene " used herein refers to aryl as above, and a hydrogen atom wherein on any position of aryl is replaced by an other binding site, forms divalent moiety thus.Arylidene can be unsubstituted or one or more, such as 1,2 or 3 identical or different radicals R ^breplaced, wherein R ^bbe selected from C ₁-C ₁₀-alkyl or halogen.Preferably, aryl is phenylene.

Term " phenylene " refers to 1,2-phenylene (adjacent phenylene), 1,3-phenylene (metaphenylene) and Isosorbide-5-Nitrae-phenylene (to phenylene).

Term " heteroaryl " (" 5 yuan to 10 yuan fragrant heterocycles of monocycle or dicyclo ") used herein refers to have 5 yuan of bicyclic heteroaryls to 6 rings, it can be fused to 5-unit, 6-unit or the ring of the first carbocyclic ring of 7-or heterocycle, there is ring element thus that add up to 8 to 10 yuan, 1,2,3 or 4 of wherein these ring elements in each case, preferably 1,2 or 3 are for being independently from each other the heteroatoms of oxygen, nitrogen and sulphur.Heteroaryl is connected to the remainder of molecule by carbocyclic unit or azo-cycle unit.Fused iso or heterocycle are selected from C ₅-C ₇-cycloalkyl, 5,6 or 7 yuan of heterocyclic radicals and phenyl.Heteroaryl can be unsubstituted or one or more, such as 1,2 or 3 identical or different radicals R ^areplaced, wherein R ^abe selected from C ₁-C ₁₀-alkyl or halogen.Preferably, aryl is phenyl.

5 yuan of examples to 6 yuan of hetero-aromatic rings of monocycle comprise triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrryl, pyrazolyl, imidazolyl, triazolyl, tetrazyl, thiazolyl, oxazolyl, thiadiazolyl group, oxadiazolyl, isothiazolyl with isoxazolyl.

The example that 5 to 6 yuan of hetero-aromatic rings are fused to (or phenyl ring is fused on 5 to 6 yuan of hetero-aromatic rings) on phenyl ring is quinolyl, isoquinolyl, indyl, indolizine base, pseudoindoyl, indazolyl, benzofuryl, benzothienyl, benzo [b] thiazolyl, benzoxazolyl, benzothiazolyl and benzimidazolyl-.5 to 6 yuan of hetero-aromatic ring examples be fused on cycloolefin ring are indolinyl, dihydro indolizine base, dihydro-iso indolyl, dihydroquinoline base, dihydro-isoquinoline base, benzopyranyl, chromanyl etc.

Term " inferior heteroaryl " used herein refers to above-mentioned heteroaryl, and a hydrogen atom wherein on any position of heteroaryl is replaced by an other binding site, forms divalent moiety thus.Inferior heteroaryl can be unsubstituted or one or more, such as 1,2 or 3 identical or different radicals R ^breplace, wherein R ^bbe selected from C ₁-C ₁₀-alkyl or halogen.

Term " heterocyclic radical " comprises and has 5 to 6 yuan of ring elements and 1,2,3 or 4 heteroatomss, and preferably 1,2 or 3 heteroatomss are as the non-aromatic saturated of ring element or the unsaturated heterocycle of part.Heterocyclic group is keyed on the remainder of molecule by carbocyclic unit or azo-cycle unit.The example of non-aromatic ring comprises pyrrolidyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuran base, dihydrofuran base, 1, 3-dioxy cyclopentyl, dioxol base, thienyl, dihydro-thiophene base, oxazolidinyl, isoxazole alkyl, oxazolinyl, isoxazoline-3-yl, thiazolinyl, isothiazoline base, thiazolidyl, isothiazole alkyl, Evil thiophene cyclopentyl, piperidyl, piperazinyl, pyranyl, dihydro pyranyl, THP trtrahydropyranyl, 1, 3 dioxy cyclopentyl and 1, 4-dioxy cyclopentyl, thiophene pyranyl, dihydro thiophene pyranyl, tetrahydrochysene thiophene pyranyl, morpholinyl, thiazinyl etc.Pyrrolidin-2-one base, tetramethyleneimine-2,5-diketo, tetrahydroglyoxaline-2-ketone group, oxazoline-2-ketone group, thiazoline-2-ketone group etc. are comprised as the example of the heterocycle of ring element containing 1 or 2 carbonyl.Heterocyclic radical can be unsubstituted or one or more, such as 1,2 or 3 identical or different radicals R ^areplaced, wherein R ^abe selected from C ₁-C ₁₀-alkyl or halogen.Preferably, aryl is phenyl.

Term " halogen " refers to fluorine, chlorine, bromine or iodine.

According to substitution pattern, the present invention's formula I used can have one or more chiral centre, and they are mixtures of corresponding isomer or non-corresponding isomer in this case.The invention provides the pure corresponding isomer of Compound I or the purposes of non-corresponding isomer or their mixture.

Polyamide polymer is herein interpreted as synthesizing the homopolymer of long-chain polyamide, multipolymer, blend and grafts, and described synthesis long-chain polyamide is in the polymer backbone containing the recurring amide radical group as main ingredient.

The example of polyamide homopolymer is nylon-6 (PA 6, polycaprolactam), nylon-7 (PA 7, poly-oenantholactam or polyenanthoamide), nylon-10 (PA 10, poly-decyl amide), nylon-11 (PA 11, poly-11 lactan), PA-12 (PA 12, nylon 12), nylon-4, 6 (PA 46, nylon 46), nylon-6, 6 (PA 66, polyhexamethylene adipamide), nylon-6, 9 (PA 69, 1, the polycondensate of 6-hexanediamine and nonane diacid), nylon-6, 10 (PA 610, 1, 6-hexanediamine and 1, the polycondensate of 10-sebacic acid), nylon-6, 12 (PA 612, 1, 6-hexanediamine and 1, the polycondensate of 12-dodecanedioic acid), nylon-10, 10 (PA1010, 1, 10-decamethylene diamine and 1, the polycondensate of 10-decane dicarboxylic acid), PA 1012 (1, the polycondensate of 10-decamethylene diamine and dodecanedicarboxylic acid) or PA 1212 (1, the polycondensate of 12-dodecamethylene diamine and dodecanedicarboxylic acid).

Polyamide copolymer can comprise the polyamide structure unit of various ratio.The example of polyamide copolymer is nylon 6/66 and nylon66 fiber/6 (namely PA6/66, PA66/6, the copolyamide be made up of PA6 and PA66 structural unit are made up of hexanolactam, hexanediamine and hexanodioic acid).PA66/6 (90/10) can comprise the PA66 of the 90% and PA6 of 10%.Other example is nylon66 fiber/610 (PA66/610 is made up of hexanediamine, hexanodioic acid and sebacic acid).

Polymeric amide also comprises partially aromatic polymeric amide.Described partially aromatic polymeric amide is usually derived from the aliphatic diamine of aromatic dicarboxylic acid as terephthalic acid or m-phthalic acid and straight or branched.Example is PA9T (being made up of terephthalic acid and nonamethylene diamine), PA6T/6l (being formed by hexanodioic acid, terephthalic acid and m-phthalic acid), PA6T/6, PA6T/6l/66 and PA6T/66.

Polymeric amide also comprises aromatic poly amide as poly(isophthaloyl metaphenylene diamine) or PPTA

Polymeric amide in principle can by two kinds of method preparations.In a polyreaction, be polymerized preparation by diprotic acid and diamine and amino acid or their derivative (as amino-nitrile, carbamyl amine, aminocarboxylic acid ester or aminocarboxylate), the amino of initial monomers or starting oligomer and carboxyl end groups react to form amide group and water each other.Water can be removed subsequently from polymkeric substance.In the polyreaction by methane amide, the amino of initial monomers or starting oligomer and amide group end group react to form amide group and ammonia each other.Ammonia can be removed subsequently from polymkeric substance.This polyreaction is commonly called polycondensation.

Polyaddition reaction is commonly referred to as the polymerization of initial monomers or starting oligomer by lactan.

Polymeric amide comprises the multipolymer be made up of polymeric amide and other segment further, and described segment is such as the form of the form, particularly polyesteramide of glycol, polyethers, ether etc., polyether ester amides or polyetheramides.Such as, in polyetheramides, polyamide segment can be any commercially available polymeric amide, preferred PA6 or PA66 and polyethers normally polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol.

Polymeric amide is preferably semicrystalline polyamides, and it is selected from aliphatic polyamide, partially aromatic polymeric amide and composition thereof.According to a concrete aspect, polyamide resin is selected from PA 6, PA 7, PA 10, PA 11, PA 12, PA 66, PA 69, PA 610, PA 612, PA 1010, PA 6/66, PA 66/6, PA 66/610 and composition thereof.According to an aspect more specifically, polymeric amide is selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66.Especially, polymeric amide is PA 6.

Below about the note of the variable (substituting group) of formula I and the preferred embodiment of index to itself and preferably to be combined with each other be all effective.X be 2 or 3, Z can be identical or different, these those skilled in the art are clearly.

One embodiment of the invention relate to purposes and method, wherein in formula I, and variable R ¹, R ², Z and x have following implication separately individually or in combination:

X is 1,2 or 3;

R ¹and R ²be independently from each other straight chain C ₁-C ₇-alkyl, side chain C ₃-C ₁₀-alkyl, unsubstituted or replace C ₃-C ₁₂-cycloalkyl, unsubstituted or replace C ₃-C ₁₂-cycloalkyl-C ₁-C ₄-alkyl, unsubstituted or replace aryl and unsubstituted or replace aryl-C ₁-C ₄-alkyl; With

Z is selected from C ₃-C ₁₀-alkane two base, unsubstituted or replace arylidene, unsubstituted or replace arylidene-C ₁-C ₄-alkylene-arylene, unsubstituted or replace inferior heteroaryl, unsubstituted or replace inferior heteroaryl-C ₁-C ₄-alkylidene group-inferior heteroaryl, unsubstituted or replace C ₅-C ₈-cycloalkylidene, unsubstituted or replace C ₅-C ₈-cycloalkylidene-C ₁-C ₄-alkylidene group-C ₅-C ₈-cycloalkylidene, unsubstituted or replace sub-Heterocyclylalkyl and unsubstituted or replace sub-Heterocyclylalkyl-C ₁-C ₄-alkylidene group-Ya Heterocyclylalkyl.

A preferred embodiment of the present invention relates to purposes and method, wherein in formula I, and variable R ¹, R ², Z and x have following implication separately individually or in combination:

X is 1,2 or 3, preferably 1 or 2, particularly 1;

R ¹and R ²be independently from each other hydrogen, side chain C ₃-C ₁₀-alkyl, C ₅-C ₁₂-cycloalkyl, C ₅-C ₁₂-cycloalkyl, C ₅-C ₁₂-cycloalkyl-C ₁-C ₄-alkyl, aryl and aryl-C ₁-C ₄-alkyl, each ring in the four kinds of groups wherein in the end mentioned is unsubstituted or by one or more identical or different radicals R ^areplace, wherein Ra is selected from C ₁-C ₁₀-alkyl and halogen.

More preferably, R ¹and R ²be independently from each other hydrogen, side chain C ₃-C ₁₀-alkyl, C ₅-C ₁₂-cycloalkyl, C ₅-C ₁₂-cycloalkyl, C ₅-C ₁₂-cycloalkyl-C ₁-C ₄-alkyl, phenyl and phenyl-C ₁-C ₄-alkyl, each ring in the four kinds of groups wherein in the end mentioned is unsubstituted or is replaced by one or more identical or different radicals R a, and wherein Ra is selected from C ₁-C ₁₀-alkyl and halogen.

Especially, R ¹and R ²be independently from each other hydrogen, side chain C ₃-C ₁₀-alkyl, its secondary carbon(atom) by alkyl or tertiary carbon atom are keyed on skeleton, unsubstituted or by 1 or 2 R ^athe C that group replaces ₅-C ₁₀-cycloalkyl, and unsubstituted or by 1 or 2 R ^athe phenyl that group replaces.

R ¹and R ²suitable example is hydrogen, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, 1-methyl-propyl, 1-ethyl propyl, 1,1-dimethyl propyl, 2-methyl butyl, 1,5-dimethylhexanyl, 1,1,3,3-tetramethyl butyl, 1-adamantyl, 2-adamantyl, high adamantyl, cyclopentyl, cyclohexyl, cyclopentyl-methyl, 1-cyclopentyl ethyl, 2-cyclopentyl ethyl, cyclohexyl methyl, 1-cyclohexyl-ethyl, 2-cyclohexyl-ethyl, by 1 or 2 C ₁-C ₄-alkyl replace cyclopentyl, by 1 or 2 C ₁-C ₄the cyclohexyl that-alkyl replaces, phenyl, tolyl or 3,4-3,5-dimethylphenyl.Especially, R ¹and R ²be selected from hydrogen, sec.-propyl, the tertiary butyl, 1-methyl-propyl, 1-ethyl propyl, 1,1-dimethyl propyl, 2-methyl butyl, 1,5-dimethylhexanyl, 1,1,3,3-tetramethyl butyl and 1-adamantyl.

Z is C ₅-C ₈-alkylidene group, C ₅-C ₇-cycloalkylidene, C ₅-C ₇-cycloalkylidene-CH ₂-C ₅-C ₇-cycloalkylidene, phenylene or phenylene-CH ₂-phenylene, each ring in the four kinds of groups wherein in the end mentioned is unsubstituted or identical or different radicals R by one or two ^breplace, wherein R ^bc ₁-C ₁₀-alkyl and halogen.

Z preferably 1,5-penta 2 base, 1,6-dihexyl, 1,7-heptan two base, cis 1,2-ring penta 2 base, trans 1,2-ring penta 2 base, cis 1,3-ring penta 2 base, trans 1,3-ring penta 2 base, wherein last-mentioned 4 groups are unsubstituted or with 1 or 2 C ₁-C ₄-alkyl, cis 1,2-ring dihexyl, trans 1,2-ring dihexyl, cis 1,3-ring dihexyl, trans 1,3-ring dihexyl, cis Isosorbide-5-Nitrae-ring dihexyl, trans Isosorbide-5-Nitrae-ring dihexyl, wherein last-mentioned 6 groups are unsubstituted or with 1 or 2 C ₁-C ₄-alkyl, 1,2-phenylene, 1,3-phenylene, Isosorbide-5-Nitrae-phenylene, wherein last-mentioned 3 groups are unsubstituted or with 1 or 2 C ₁-C ₄-alkyl;

Wherein # is the keyed jointing point being connected to internal N atom in urea part;

Especially, Z is anti-form-1,4-ring dihexyl.Especially, if x is 2, then each Z has identical implication.

The present invention's preferred embodiment relates to purposes and method, wherein in formula I, and R ¹and R ²there is different implications.Another preferred embodiment of the present invention relates to purposes and method, wherein in formula I, and R ¹and R ²there is identical implication.

A particularly preferred embodiment of the present invention relates to purposes and method, the variable R of its compounds of formula I ¹, R ², Z and x have following implication:

R ¹and R ²there is identical implication and be selected from 1,1-dimethyl propyl, 1,5-dimethylhexanyl, 1,1,3,3-tetramethyl butyl and 1-adamantyl;

Z is trans Isosorbide-5-Nitrae-ring dihexyl; With

X is 1.

Another particularly preferred embodiment of the present invention relates to purposes and method, the variable R of its compounds of formula I ¹, R ²be all hydrogen, Z is trans Isosorbide-5-Nitrae-ring dihexyl, and x is 1.

The present invention's particularly preferred embodiment relates to purposes and method, and wherein polyamide resin is selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66, in formula I, and R ¹and R ²be identical and be selected from the tertiary butyl, 1,1-dimethyl propyl, 1,5-dimethylhexanyl, 1,1,3,3-tetramethyl butyl and 1-adamantyl; Z is trans Isosorbide-5-Nitrae-cyclohexylidene; X is 1.

Another particularly preferred embodiment of the present invention relates to purposes and method, and wherein polyamide resin is selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66, R in formula I ¹and R ²be hydrogen; Z is trans Isosorbide-5-Nitrae-cyclohexylidene; X is 1.

Formula I is as known in the art or prepares by the standard method of similar this area or prepared by the method described in the application's experimental section.

X is that the formula I of 1 is also referred to as double urea compound I.

X is that the formula I of 2 is also referred to as triuret Compound I.

X is that the formula I of 3 is also referred to as four carbamide compound I.

Such as, formula I, wherein x is 1, R ¹and R ²there is identical implication, its scheme 1 and 2 as described below and preparing.

Scheme 1:

In scheme 1, define Z and R ¹.The diamine compound of formula II and the isocyanic ester III of 2 equivalents react and with good productive rate production I.This reaction is normally carried out in organic solvent.Suitable solvent is that polar aprotic solvent is as tetrahydrofuran (THF).

Or formula I double urea compound can be reacted by the amine of the diisocyanate cpd of formula IV and formula V and prepare.This reaction is normally carried out in organic solvent.Suitable solvent is that polar aprotic solvent is as tetrahydrofuran (THF).

Scheme 2:

In scheme 2, Z and R ¹as defined above.

Formula I, wherein x is 1, and R ¹and R ²have different implications, it can be prepared by scheme 3 shown below.

Scheme 3:

In scheme 3, Z, R ¹and R ²as defined above.Use the isocyanic ester process formula VI of formula VII and III and the amine compound of VIa respectively, obtain formula I with good yield respectively.This reaction is carried out usually in organic solvent.Suitable solvent is that polar aprotic solvent is as N-Methyl pyrrolidone.

Three carbamide compounds of formula I, i.e. formula I, wherein x is 2, R ¹have and R ²identical implication, can prepare as shown in Scheme 4.

Scheme 4:

In scheme 4, Z and R ¹definition described above.Hal is halogen, and Hal ' is halogen.Preferably, Hal and Hal ' is chlorine.

Step I in scheme 4) in, the isocyanic ester III of diamines II and monovalent reacts to obtain amine compound X.This reaction can be similar to be carried out with the mode of the step described in scheme 1.Step I i in scheme 4) in, the dihalide carbonyl (carbonyl dihalide) of an amine compound X and formula XI reacts to obtain triuret Compound I.

Three carbamide compounds of formula I, the i.e. compound of formula I, wherein x is 2, R ¹have and R ²identical implication, can prepare by shown in scheme 5.

Scheme 5:

In scheme 5, R ¹as defined above and Z as defined above, be preferably cycloalkylidene or arylidene.

Step I in scheme 5) in, diamine compound XII and isocyanate compound XIII reacts to obtain dinitro compound XIV.This reaction can be similar to the step I of scheme 4) described in method carry out.Step I i in scheme 5) in, dinitro compound XIV is reduced to diamino compound XV.Described reduction can be carried out with hydrazine hydrate under Pd/C catalyzer exists.Step I ii in scheme 5) in, be obtained by reacting triuret Compound I between the isocyanate compound III of diamino compound XV and 2 equivalents.

Four carbamide compounds of formula I, i.e. formula I, wherein x is 3, and R ¹have and R ²identical implication, can by preparing shown in scheme 6.

Scheme 6:

In scheme 6, R ¹define as mentioned above with Z.R ¹identical or different implication can be had.Z can have identical or different implication.Amino-complex XI be similar to the step described in scheme 2 and diisocyanate cpd IV reacts.

Polyamide resin containing one or more other component, such as, is selected from following component: tinting material, antioxidant, uv-absorbing agent, photostabilizer, strongthener, filler, antifogging agent, releasing agent, biocide, static inhibitor and rheology modifier usually.The example of the other component that can comprise in the compositions of the present invention comprises following:

1. tinting material

Term tinting material comprises dyestuff and pigment.Pigment can be the pigment of organic or inorganic known in the art.Suitable pigment example is colorant, pearly pigment, such as special effect pigment or the pigment based on liquid crystalline polymers.

Tinting material can be dyestuff.The organic compound demonstrating fluorescence in the visibility region of electromagnetic spectrum is also considered as tinting material, as fluorescence dye or white dyes.Tinting material can also have other characteristic as electroconductibility, or magnetic shielding.

Suitable dyestuff is all dyestuffs that can be dissolved in polyamide polymer composition.The example of suitable dyestuff is azoic dyestuff, pyrazolone dye, anthraquinone dye, cyclic ketones dyestuff, perylene based dye, indigo and thioindigo(id)dyes, and azomethine dyes.

2. antioxidant

2.1 alkylating single phenol, such as 2, 6-bis--tert-butyl-4-methyl-Phenol, the 2-tertiary butyl-4, 6-xylenol, 2, 6-bis--tertiary butyl-4-ethylphenol, 2, 6-bis--tertiary butyl-4-normal-butyl phenol, 2, 6-bis--tertiary butyl-4-isobutyl-phenol, 2, 6-bicyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4, 6-xylenol, 2, 6-bis-(octadecyl)-4-methylphenol, 2, 4, 6-thricyclohexyl phenol, 2, 6-bis--tertiary butyl-4-methoxymetllyl-phenol, side chain is the nonylphenol of straight or branched, such as 2, 6-dinonyl-4-methylphenol, 2, 4-dimethyl-6-(1'-methylundecane-1'-base) phenol, 2, 4-dimethyl-6-(1'-methyl heptadecane-1'-base) phenol, 2, 4-dimethyl-6-(1'-methyltridec-1'-base) phenol and composition thereof.

2.2 Alkylthiomethylphenols, such as: 2,4-dioctylthiomethyl-6-tert.-butyl phenol, 2,4-dioctylthiomethyl-6-methylphenols, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-bis-(dodecylthiomethyl)-4-nonylphenol.

2.3 quinhydrones and alkylating quinhydrones, such as: 2,6-di-t-butyl-4-methoxyphenol, 2,5 di tert butylhydroquinone, 2,5 di tert amlyl hydroquinone, 2,6-phenylbenzene-4-octade-cyloxyphenol, 2,6-di-tert-butyl hydroquinone, 2,5-di-t-butyls-4-hydroxyanisol, 3,5-di-t-butyls-4-hydroxyanisol, stearic acid 3,5-di-tert-butyl-hydroxy phenyl ester, hexanodioic acid two (3,5-di-tert-butyl-hydroxy phenyl) ester.

2.4 tocopherols, such as alpha-tocopherol, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol and composition thereof (vitamin-E).

2.5 hydroxylated thiodiphenyl ethers, such as 2,2'-sulfydryl two (the 6-tertiary butyl-4-cresylol), 2,2'-sulfydryl two (4-octyl phenol), 4,4'-sulfydryls are two-and (the 6-tertiary butyl-3-cresylol), 4,4'-sulfydryls are two-(the 6-tertiary butyl-2-cresylol), 4,4'-sulfydryl two-(3,6-bis--sec.-amyl sec-pentyl secondary amyl phenol), 4,4'-two (2,6-dimethyl-4-hydroxyphenyl) disulphide.

2.6 alkylidene diphenyl phenol, such as 2,2'-methylene-biss (the 6-tertiary butyl-4-cresylol), 2,2'-methylene-bis (the 6-tertiary butyl-4-ethylphenol), 2,2'-methylene-bis [4-methyl-6 (Alpha-Methyl cyclohexyl)-phenol], 2,2'-methylene-bis (4-methyl-6 cyclohexylphenol), 2,2'-methylene-bis (6-nonyl-4-methylphenol), 2,2'-methylene-bis (4,6-DI-tert-butylphenol compounds), 2,2'-ethylenebis (4,6-DI-tert-butylphenol compounds), 2,2'-ethylenebis (the 6-tertiary butyl-4-isobutyl-phenol), 2,2'-methylene-bis [6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis [6-(α, alpha, alpha-dimethyl benzyl)-4-nonylphenol], 4,4'-methylene-bis (2,6 di t butyl phenol), 4,4'-methylene-bis (the 6-tertiary butyl-2-methylphenol), two (5-tertiary butyl-4-hydroxy-2-tolyl) butane of 1,1'-, two (the 3-tertiary butyl-5-methyl-2-the acrinyl)-4-cresylol of 2,6-, 1,1,3-tri-(5-tertiary butyl-4-hydroxy-2-tolyl) butane, two (5-tertiary butyl-4-hydroxy-2-the tolyl)-3-n-dodecane sulfydryl butane of 1,1-, ethylene glycol bis [two (the 3'-tertiary butyl-4'-hydroxyphenyl) butyric ester of 3,3-], two (3-tertiary butyl-4-hydroxy-5-methylphenyl) Dicyclopentadiene (DCPD), two [2-(the 3'-tertiary butyl-2'-hydroxyl-5'-the xylyl)-6-tertiary butyl-4-tolyl] terephthalate, 1,1-pair-(3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-pair-(3,5-, bis--tertiary butyl-4-hydroxyphenyl) propane, 2,2-pair-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-4-n-dodecane sulfydryl butane, 1,1,5,5-tetra-(5-tertiary butyl-4-hydroxy-2-tolyl) pentane.

2.7 O-, N-and S-benzyl compounds, such as 3,5,3', 5'-tetra--tertiary butyl-4,4'-dihydroxyl dibenzyl ether, octadecyl-4-hydroxyl-3,5-dimethylbenylmercaptoacetate, tridecyl-4-hydroxyl-3,5-di-t-butyl Benzylmercapto acetic ester, three (3,5-di-tert-butyl-4-hydroxyl benzyl) amine, two (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) dithio terephthalate, two (3,5 di-tert-butyl-4-hydroxyl benzyl) sulfide, iso-octyl-3,5-di-tert-butyl-4-hydroxyl benzyl mercaptoacetate.

The malonic ester of 2.8 hvdroxvbenzvl, such as two octadecyl-2,2-two (3,5-bis--tertiary butyl-2-acrinyl) malonic ester, two octadecyl-2-(3-tertiary butyl-4-hydroxy-5-xylyl) malonic ester, two didodecylmercaptoethyl-2,2-two (3,5-bis--tertiary butyl-4-acrinyl) malonic ester, two [4-(1,1,3,3-tetramethyl butyl) phenyl]-2, two (3,5-, the bis--tertiary butyl-4-acrinyl) malonic ester of 2-.

2.9 Aromatic hydroxybenzyl compounds, such as 1,3,5-tri-(3,5-, bis--tertiary butyl-4-acrinyl)-2,4,6-Three methyl Benzene, Isosorbide-5-Nitrae-bis-(3,5-, bis--tertiary butyl-4-acrinyl)-2,3,5,6-tetramethyl-benzene, 2,4,6-tri-(3,5-, bis--tertiary butyl-4-acrinyl) phenol.

2.10 triaizine compounds, such as 2, two (the octylmercapto)-6-(3 of 4-, 5-bis--tertiary butyl-4-hydroxy anilino)-1, 3, 5-triazine, 2-octylmercapto-4, 6-two (3, 5-bis--tertiary butyl-4-hydroxy anilino)-1, 3, 5-triazine, 2-octylmercapto-4, 6-two (3, 5-bis--tertiary butyl-4-hydroxy phenoxy group)-1, 3, 5-triazine, 2, 4, 6-tri-(3, 5-bis--tertiary butyl-4-hydroxy phenoxy group)-1, 2, 3-triazine, 1, 3, 5-tri-(3, 5-bis--tertiary butyl-4-hydroxy benzyl) isocyanuric acid ester, 1, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, 6-dimethyl benzyl) isocyanuric acid ester, 2, 4, 6-tri-(3, 5-bis--tert-butyl-hydroxy phenyl ethyl)-1, 3, 5-triazine, 1, 3, 5-tri-(3, 5-bis--tert-butyl-hydroxy phenyl propionyl) six hydrogen-1, 3, 5-triazine, 1, 3, 5-tri-(3, 5-dicyclohexyl-4-acrinyl) isocyanuric acid ester.

2.11 benzylphosphonic acid ester, such as: dimethyl-2,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, diethyl-3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, two (octadecyls)-3, the calcium salt of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, two (octadecyl)-5-tertiary butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl esters.

2.12 BS-749, such as 4-hydroxylauranilide, 4-hydroxystearanilide, N-(3,5-di-tert-butyl-hydroxy phenyl) carbamic acid octyl ester.

2.13 β-(3, 5-di-tert-butyl-hydroxy phenyl) ester of propionic acid and following monohydroxy-alcohol or polyvalent alcohol, described monohydroxy-alcohol or polyhydric alcohols are as methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1, 6-hexylene glycol, 1, 9-nonanediol, ethylene glycol, 1, 2-propylene glycol, neopentyl glycol, sulphur Diethylene Glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N'-bis-(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapenta, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2, 6, 7-trioxa-l-phosphabicyclo [2.2.2] octane.

The ester of 2.14 β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and following monohydroxy-alcohol or polyvalent alcohol, described monohydroxy-alcohol or polyhydric alcohols are as methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1, 6-hexylene glycol, 1, 9-nonanediol, ethylene glycol, 1, 2-propylene glycol, neopentyl glycol, sulphur Diethylene Glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N'-bis-(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapenta, trimethylammonium hexylene glycol, trimethyl propane, 4-methylol-1-phospha-2, 6, 7-trioxa-l-phosphabicyclo [2.2.2] octane, 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1,1-dimethyl ethyl]-2,4,8,10-tetra-oxaspiro [5.5]-undecanes.

2.15 β-(3, 5-dicyclohexyl-4-hydroxy phenyl) ester of propionic acid and following monohydroxy-alcohol or polyvalent alcohol, described monohydroxy-alcohol or polyhydric alcohols are as methyl alcohol, ethanol, octanol, stearyl alcohol, 1, 6-hexylene glycol, 1, 9-nonanediol, ethylene glycol, 1, 2-propylene glycol, neopentyl glycol, sulphur Diethylene Glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N'-bis-(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapenta, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2, 6, 7-trioxa-l-phosphabicyclo [2.2.2] octane.

2.16 3, the ester of 5-di-tert-butyl-hydroxy phenyl acetic acid and following monohydroxy-alcohol or polyvalent alcohol, described monohydroxy-alcohol or polyhydric alcohols are as methyl alcohol, ethanol, octanol, stearyl alcohol, 1, 6-hexylene glycol, 1, 9-nonanediol, ethylene glycol, 1, 2-propylene glycol, neopentyl glycol, sulphur Diethylene Glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, two (hydroxyethyl) oxalic acid diamide of N'-, 3-thiaundecanol, 3-thiapenta, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2, 6, 7-trioxa-l-phosphabicyclo [2.2.2] octane.

2.17 β-(3; 5-di-tert-butyl-hydroxy phenyl) amides of propionic acid; such as: N; N'-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) hexa-methylene diamide, N; N'-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) trimethylenediamide, N; N'-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) hydrazides, N; two [2-(3-[3, the 5-di-tert-butyl-hydroxy phenyl] propionyloxy) ethyl] oxalic acid diamide (Naugard of N'- ^tMxL-1, is provided by Uniroyal).

2.18 xitix (vitamins C)

2.19 amine antioxidantss, such as: N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis-(Isosorbide-5-Nitrae-dimethyl amyl group)-p-phenylenediamine, N, N'-bis-(1-ethyl-3-methyl amyl)-p-phenylenediamine, N, N'-bis-(1-methylheptyl)-p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-phenylbenzene-p-phenylenediamine, N, N'-bis-(2-naphthyl)-p-phenylenediamine, N-sec.-propyl-N'-Phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-Phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-Phenyl-p-phenylenediamine, N-cyclohexyl-N'-Phenyl-p-phenylenediamine, 4-(p-amino toluene alkylsulfonyl) pentanoic, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, pentanoic, N-allyl group pentanoic, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(the tertiary octyl phenyl of 4-)-naphthalidine, N-phenyl-2-naphthylamine, octylatcd pentanoic, the such as tertiary octyl diphenylamine of p, p'-bis-, 4-normal-butyl-amino-phenol, 4-acylamino phenol, 4-nonanoyl aminophenol, 4-dodecanoylamino phenol, 4-stearyl amino-phenol, two (4-p-methoxy-phenyl) amine, 2,6-di-t-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenyl-methane, 4,4'-diaminodiphenyl-methane, N, N, N', N'-tetramethyl--4,4'-diaminodiphenyl-methane, 1,2-bis-[(2-aminomethyl phenyl) is amino] ethane, 1,2-bis-(phenyl amino) propane, (o-tolyl) biguanides, two [4-(1', 3'-dimethylbutyl) phenyl] amine, tertiary octylatcd N-phenyl-1-naphthylamine, the mixture of the tertiary butyl/tertiary octyl diphenylamine of monoalkylation and di, the mixture of the nonyl diphenylamine of monoalkylation and di, the mixture of the dodecyl diphenylamine of monoalkylation and di, the mixture of the sec.-propyl/isohexyl-pentanoic of monoalkylation and di, the mixture of the tert-butyl diphenylamine of monoalkylation and di, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, thiodiphenylamine, the mixture of the tertiary butyl/tertiary octyl group thiodiphenylamine of monoalkylation and di, the mixture of the tertiary octyl group thiodiphenylamine of monoalkylation and di, N-allyl group thiodiphenylamine, N, N, N', N'-tetraphenyl-Isosorbide-5-Nitrae-diamino but-2-ene, N, N-bis-(2,2,6,6-tetramethyl piperidine-4-base)-hexamethylene-diamine, two (2,2,6,6-tetramethyl piperidine-4-base) sebate, 2,2,6,6-tetramethyl piperidine-4-ketone, 2,2,6,6-tetramethyl piperidine-4-alcohol.

3. uv-absorbing agent and photostabilizer

3.1 2-(2'-hydroxy phenyl) benzotriazole category, such as: 2-(2'-hydroxyl-5'-aminomethyl phenyl) benzotriazole, 2-(3', 5'-di-t-butyl-2'-hydroxy phenyl) benzotriazole, 2-(the 5'-tertiary butyl-2'-hydroxy phenyl) benzotriazole, 2-(2'-hydroxyl-5'-(1, 1, 3, 3-tetramethyl butyl) phenyl) benzotriazole, 2-(3', 5'-di-t-butyl-2'-hydroxy phenyl)-5-chlorobenzotriazole, 2-(the 3'-tertiary butyl-2'-hydroxyl-5'-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(the 3'-sec-butyl-5'-tertiary butyl-2'-hydroxy phenyl) benzotriazole, 2-(2'-hydroxyl-4'-octyloxyphenyl) benzotriazole, 2-(3', 5'-bis-tert-pentyl-2'-hydroxy phenyl) benzotriazole, 2-(3', 5'-bis-(α, α-dimethylbenzyl)-2'-hydroxy phenyl) benzotriazole, 2-(the 3'-tertiary butyl-2'-hydroxyl-5'-(2-octoxycarbonylethyl) phenyl)-5-chlorobenzotriazole, 2-(the 3'-tertiary butyl-5'-[2-(2-ethylhexyl oxygen base) carbonylethyl]-2'-hydroxy phenyl)-5-chlorobenzotriazole, 2-(the 3'-tertiary butyl-2'-hydroxyl-5'-(2-dion e) phenyl)-5-chlorobenzotriazole, 2-(the 3'-tertiary butyl-2'-hydroxyl-5'-(2-dion e) phenyl) benzotriazole, 2-(the 3'-tertiary butyl-2'-hydroxyl-5'-(2-octoxycarbonylethyl) phenyl) benzotriazole, 2-(the 3'-tertiary butyl-5'-[2-(2-ethyl hexyl oxy) carbonylethyl]-2'-hydroxy phenyl) benzotriazole, 2-(3'-dodecyl-2'-hydroxyl-5'-aminomethyl phenyl) benzotriazole, 2-(the 3'-tertiary butyl-2'-hydroxyl-5'-(2-iso-octyl oxygen base carbonylethyl) phenyl benzotriazole, 2'-methylene radical two [4-(1, 1, 3, 3-tetramethyl butyl)-6-benzotriazole-2-base phenol], the ester exchange offspring of 2-[the 3'-tertiary butyl-5'-(2-dion e)-2'-hydroxy phenyl]-2H-benzotriazole and Liquid Macrogol, [R-CH ₂cH ₂-COO-CH ₂cH ₂] ₂, the wherein R=3'-tertiary butyl-4'-hydroxyl-5'-2H-benzotriazole-2-base-phenyl, 2-[2'-hydroxyl-3'-(alpha, alpha-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl butyl) phenyl] benzotriazole, 2-[2'-hydroxyl-3'-(1,1,3,3-tetramethyl butyl)-5'-(alpha, alpha-dimethylbenzyl) phenyl] benzotriazole.

3.2 2-hydroxy benzophenone ketones, such as 4-hydroxyl, 4-methoxyl group, 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base, 4-dodecyloxy, 4-benzyloxy, 4,2', 4'-trihydroxyies and 2'-hydroxyl-4,4'-dimethoxy derivatives.

3.3 replace with the ester of unsubstituted M-nitro benzoic acid; such as: Whitfield's ointment 4-tert-butyl-phenyl ester, salol, Whitfield's ointment octyl octylphenyl, dibenzoyl resorcinols, two (4-tert-butyl-benzoyl) Resorcinol, benzoyl Resorcinol, 3; 5-di-t-butyl-4-Para Hydroxy Benzoic Acid 2; 4-di-tert-butyl-phenyl ester, 3; 5-di-t-butyl-4-Para Hydroxy Benzoic Acid cetyl ester, 3; 5-di-t-butyl-4-Para Hydroxy Benzoic Acid stearyl, 3; 5-di-t-butyl-4-Para Hydroxy Benzoic Acid 2-methyl-4,6-di-tert-butyl-phenyl ester.

3.4 esters of acrylic acid, such as: alpha-cyano-β, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenyl 2-Propenoic acid-2-ethylhexyl ester, α-methoxycarbonyl methyl cinnamate, alpha-cyano-Beta-methyl-p-p-Methoxymethylcinnamate, alpha-cyano-Beta-methyl-p-methoxycinnamate acid butyl ester, α-methoxycarbonyl-p-p-Methoxymethylcinnamate and N-(beta-methoxy-carbonyl-p-cyanovinyl)-2 methyl indole quinoline.

3.5 nickel compound, such as: 2,2'-sulfo-two [4-(1,1,3,3-tetramethyl butyl) phenol] nickel complex, as the complex compound of 1:1 or 1:2, there are or not have other parts as n-butylamine, trolamine or N-cyclohexyldi, nickel dibutyl dithiocarbamate; The nickel salt of mono alkyl ester, the such as methyl ester of 4-hydroxyl-3,5-di-t-butyl benzylphosphonic acid or the nickel salt of ethyl ester; The nickel complex of ketoxime, the such as nickel complex of 2-hydroxy-4-methyl phenyl-undecane base ketoxime; There is or not have the nickel complex of the 1-phenyl-4-lauroyl-5-hydroxypyrazoles of other parts.

3.6 sterically hindered amines, such as: two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, two (2, 2, 6, 6-tetramethyl--4-piperidyl) succinate, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) sebate, two (1-octyloxy-2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, normal-butyl-3, 5-di-tert-butyl-4-hydroxyl benzyl propanedioic acid two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, 1-(2-hydroxyethyl)-2, 2, 6, the condenses of 6-tetramethyl--4-hydroxy piperidine and succsinic acid, N, N'-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl) hexamethylene-diamine and the tertiary pungent amino-2 of 4-, 6-bis-chloro-1, 3, the straight chain of 5-triazine or ring-shaped condensate, three (2, 2, 6, 6-tetramethyl--4-piperidyl) nitrilotriacetate, four (2, 2, 6, 6-tetramethyl--4-piperidyl)-1, 2, 3, 4-ethylene-dimalonic acid ester, 1, 1'-(1, 2-ethylidene)-two (3, 3, 5, 5-tetramethyl-piperazinones), 4-benzoyl-2, 2, 6, 6-tetramethyl piperidine, the stearic oxygen base-2 of 4-, 2, 6, 6-tetramethyl piperidine, two (1, 2, 2, 6, 6-pentamethvl base)-2-normal-butyl-2-(2-hydroxyl-3, 5-di-t-butyl benzyl)-malonic ester, 3-n-octyl-7, 7, 9, 9-tetramethyl--1, 3, 8-thriazaspiro [4.5] decane-2, 4-diketone, two (1-octyloxy-2, 2, 6, 6-tetramethyl-piperidyl) sebate, two (1-octyloxy-2, 2, 6, 6-tetramethyl-piperidyl) succinate, N, N'-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-morpholino-2, 6-bis-chloro-1, 3, the straight chain of 5-triazine or ring-shaped condensate, 2-chloro-4, 6-bis-(4-n-butylamino-2, 2, 6, 6-tetramethyl-piperidyl)-1, 3, 5-triazine and 1, the condenses of 2-bis-(3-aminopropyl amino) ethane, 2-chloro-4, 6-bis-(4-n-butylamino-1, 2, 2, 6, 6-pentamethvl base)-1, 3, 5-triazine and 1, the condenses of 2-bis-(3-aminopropyl amino) ethane, 8-ethanoyl-3-dodecyl-7, 7, 9, 9-tetramethyl--1, 3, 8-thriazaspiro [4.5] decane-2, 4-diketone, 3-dodecyl-1-(2, 2, 6, 6-tetramethyl--4-piperidyl) tetramethyleneimine-2, 5-diketone, 3-dodecyl-1-(1, 2, 2, 6, 6-pentamethyl--4-piperidyl) tetramethyleneimine-2, 5-diketone, 4-n-Hexadecane oxygen base-and 4-octadecane oxygen base-2, 2, 6, the mixture of 6-tetramethyl piperidine, N, N'-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-Cyclohexylamino-2, 6-bis-chloro-1, 3, the condenses of 5-triazine, 1, 2-bis-(3-aminopropyl amino) ethane and 2, 4, 6-tri-chloro-1, 3, 5-triazine and 4-butyl amino-2, 2, 6, the condenses (CAS registration number [136504-96-6]) of 6-tetramethyl piperidine, the condenses (CAS registration number [192268-64-7]) of 1,6-hexanediamine and 2,4,6-tri-chloro-1,3,5-triazines and N, N-dibutylamine and 4-butyl amino-2,2,6,6-tetramethylpiperidine, N-(2, 2, 6, 6-tetramethyl--4-piperidyl)-dodecyl succinimide, N-(1, 2, 2, 6, 6-pentamethyl--4-piperidyl)-dodecyl succinimide, 2-undecyl-7, 7, 9, 9-tetramethyl--1-oxa--3, 8-diaza-4-oxo-spiral shell [4, 5] decane, 7, 7, 9, 9-tetramethyl--2-ring undecyl-1-oxa--3, 8-diaza-4-oxo spiral shell-[4, 5] reaction product of decane and Epicholorohydrin, 1, 1-bis-(1, 2, 2, 6, 6-pentamethyl--4-piperidyl oxygen base carbonyl)-2-(4-p-methoxy-phenyl) ethene, N, N'-diformyl-N, N'-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl) hexamethylene-diamine, 4-methoxymethylene propanedioic acid and 1, 2, 2, 6, the diester of 6-pentamethyl--4-hydroxy piperidine, poly-[methyl-propyl-3-oxygen base-4-(2, 2, 6, 6-tetramethyl--4-piperidyl)] siloxanes, maleic anhydride-alpha-olefin copolymer and 2, 2, 6, 6-tetramethyl--4-amino piperidine or 1, 2, 2, 6, the reaction product of 6-pentamethyl--4-amino piperidine.

3.7 Oxamides, such as: 4, 4'-bis-octyloxy butoxanilide, 2, 2'-diethoxy butoxanilide, 2, 2'-bis-octyloxy-5, 5'-bis-tert-butoxanilide, 2, 2'-bis-(dodecyloxy)-5, 5'-bis-tert-butoxanilide, 2-oxyethyl group-2'-ethyloxanilide, N, N'-bis-(3-dimethylamino-propyl) oxalic acid diamide, 2-oxyethyl group-5-the tertiary butyl-2'-oxyethyl group butoxanilide and itself and 2-oxyethyl group-2'-ethyl-5, the mixture of 4'-bis-tert-butoxanilide, the mixture of o-and p-methoxyl group-dibasic butoxanilide, and the mixture of o-and p-oxyethyl group-dibasic butoxanilide.

3.8 2-(2-hydroxyphenyl)-1, 3, 5-triazines, such as 2, 4, 6-tri-(2-hydroxyl-4-octyloxyphenyl)-1, 3, 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-(2, 4-dihydroxy phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2, two (2-hydroxyl-4-the propoxyphenyl)-6-(2 of 4-, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (the 4-tolyl)-1 of 6-, 3, 5-triazine, 2-(2-hydroxyl-4-dodecyloxy phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-(2-hydroxyl-4-tridecane oxygen base phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy propoxy) phenyl]-4, 6-two (2, 4-dimethyl)-1, 3, 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy propoxy-) phenyl]-4, 6-two (2, 4-dimethyl)-1, 3, 5-triazine, 2-[4-(dodecyloxy/tridecane oxygen base-2-hydroxy propyloxy group)-2-hydroxyphenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-dodecyloxy propoxy-) phenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-(2-hydroxyl-4-hexyloxy) phenyl-4, 6-phenylbenzene-1, 3, 5-triazine, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4, 6-phenylbenzene-1, 3, 5-triazine, 2, 4, 6-tri-[2-hydroxyl-4-(3-butoxy-2-hydroxy propyloxy group) phenyl]-1, 3, 5-triazine, 2-(2-hydroxyphenyl)-4-(4-p-methoxy-phenyl)-6-phenyl-1, 3, 5-triazine, 2-{2-hydroxyl-4-[3-(2-ethylhexyl-1-oxygen)-2-hydroxy propyloxy group] phenyl } 4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine.

4. metal passivator; such as: N; N'-bis, N-bigcatkin willow aldehyde radical-N'-salicyloyl hydrazine, N; N'-two (salicyloyl) hydrazine, N; N'-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine, 3-salicylyl amino-1; 2; 4-triazole, two (sub-phenmethyl) oxalyl two hydrazine, butoxanilide, isophthaloyl two hydrazine, sebacoyl phenylbenzene hydrazides, N; N'-diacetyl adipyl dihydrazide, N; two (salicyloyl) oxalyl two hydrazine of N'-, two (salicyloyl) sulfo-propionyl two hydrazine of N, N'-.

5. phosphorous acid esters and phosphiinic acid ester, such as: triphenyl phosphite, phosphorous acid diphenyl alkyl ester, phenyl dialkyl, tricresyl phosphite (nonyl phenyl) ester, trilauryl, tricresyl phosphite (octadecyl) ester, diphosphorous acid two (octadecyl) pentaerythritol ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, diphosphorous acid diiso decyl pentaerythritol ester, diphosphorous acid two (2,4-di-tert-butyl-phenyl) pentaerythritol ester, diphosphorous acid two (2,4-dicumylphenyl) pentaerythritol ester, diphosphorous acid two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol ester, diphosphorous acid two isodecyl oxygen base pentaerythritol ester, diphosphorous acid two (2,4-di-t-butyl-6-aminomethyl phenyl)-pentaerythritol ester, diphosphorous acid two (2,4,6-tri-(tert-butyl-phenyl) pentaerythritol ester, three tricresyl phosphite stearyl sorbitol esters, two phosphonous acid four (2,4-di-tert-butyl-phenyl) 4,4'-diphenylene esters, 6-iso-octyl oxygen base-2,4,8,10-tetra-tert-12H-dibenzo [d, g]-1,3,2-dioxaphosphepin eight ring, phosphorous acid two (2,4-di-t-butyl-6-aminomethyl phenyl) methyl ester, phosphorous acid two (2,4-di-t-butyl-6-aminomethyl phenyl) ethyl ester, fluoro-2,4,8,10-tetra-tert-12-methyl-dibenzo [d, g]-1,3,2-dioxaphosphepin eight rings of 6-, 2,2', 2 "-nitrilo-[triethyl three (3,3', 5,5'-tetra-terts-1, 1'-phenylbenzene-2,2'-bis-base) phosphorous acid ester], 2-ethylhexyl (3,3', 5,5'-tetra-tert-1,1'-phenylbenzene-2,2'-bis-base) phosphorous acid ester, 5-butyl-5-ethyl-2-(2,4,6-tri-butyl-phenoxy)-1,3,2-dioxaphosphepin cyclopropane.

6. phosphorous acid, phosphorous hydrochlorate, phosphorous acid esters or derivatives thereof:

Phosphorous acid comprises the oxygen acid of phosphorus as phosphoric acid, phosphonic acids and Hypophosporous Acid, 50.The suitable salt of phosphorous acid is an alkali metal salt, alkaline earth salt or transition metal salt.Wherein, preferred calcium salt, barium salt, magnesium salts, sodium salt, sylvite, manganese salt and aluminium salt.Particularly preferably be sodium hypophosphite (NaPO ₂h ₂, be also known as sodium dihydric hypophosphite), two (Hypophosporous Acid, 50) manganese (Mn (H ₂pO ₂) ₂, be also known as Hypophosporous Acid, 50 dihydro manganese (II)), hypo-aluminum orthophosphate (Al (H ₂pO ₂) ₃) and composition thereof.Particularly preferably be phosphonic acid ester, half ester and composition thereof equally, particularly hydroxyl Cphenyl-alkyl phosphonic acid ester, half ester or its mixture, such as be disclosed in WO2007006647 those, particularly two [single ethyl (3,5-di-tert-butyl-4-hydroxyl benzyl) phosphonic acids] calcium ( 195, by BASF SE commercially), or (3,5-di-tert-butyl-4-hydroxyl benzyl) diethyl phosphonate ( 295, by BASF SE commercially).

7. azanol class, such as: N, N-dibenzyl hydroxylamine, N, N-diethyl hydroxylamine, N, N-Ndioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-bis-(tetradecyl) azanol, N, N-bis-(hexadecyl) azanol, N, N-bis-(octadecyl) azanol, N-hexadecyl-N-octadecyl base azanol, N-heptadecyl-N-octadecyl hydroxylamine, N derived from hydrogenated tallow amine, N-dialkylhydroxyamines.

8. nitrone class, such as: N-benzyl-alpha-phenyinitrone, N-ethyl-α-methylnitrone, N-octyl alpha-heptylnitrone, N-lauryl-α-undecyinitrone, N-tetradecyl-α-tridecyinitrone, N-hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecyl-nitrone, N-hexadecyl-al-pha nitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecyl-nitrone, N-octadecyl-α-hexadecyl nitrone, the nitrone derived by the N derived from hydrogenated tallow amine, N-dialkylhydroxyamines.

9. thiosynergistic, such as thiodipropionate dilauryl or thio-2 acid distearyl ester.

10. Peroxide scavengers, the such as ester of p-thio-2 acid, such as Lauryl Ester, stearyl, myristyl ester or tridecyl ester; The zinc salt of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, two (octadecyl) disulphide, four (p-dodecy) propionate.

11. Polvamide stabilisers, such as: the mantoquita be combined with iodide and/or phosphorus compound and manganous salt.

12. Basic co-stabilisers, such as: an alkali metal salt of trimeric cyanamide, polyvinylpyrrolidone, Dyhard RU 100, cyanuric acid alkatriene propyl diester, urea derivatives, hydrazine derivative, amine, polymeric amide, urethane, higher fatty acid and alkaline earth salt, such as calcium stearate, Zinic stearas, behenic acid magnesium, Magnesium Stearate, sodium ricinoleate and potassium palmitate, pyrocatechuic acid antimony or pyrocatechuic acid zinc.Polyamide resin does not preferably comprise barium stearate.

13. other additives, such as: softening agent, lubricant, flow control agent, fireproofing agent, releasing agent and whipping agent.

14. Benzopyranone kinds and indole ketone, such as those compounds: US-A-4 disclosed in following patent, 325,863, US-A-4,338,244, US-A-5,175,312, US-A-5,216,052, US-A-5,252,643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)-phenyl]-5, 7-di-t-butyl benzo furans-2-ketone, 5, 7-di-t-butyl-3-[4-(2-stearoyl keto base oxethyl) phenyl]-benzofuran-2-ones, 3, 3'-bis-[5, 7-di-t-butyl-3-(4-[2-hydroxyl-oxethyl] phenyl) benzofuran-2-ones], 5, 7-di-t-butyl-3-(4-ethoxyl phenenyl) benzofuran-2-ones, 3-(4-acetoxy-3, 5-3,5-dimethylphenyl)-5, 7 di-t-butyl benzo furans-2-ketone, 3-(3, 5-dimethyl-4-new pentane acyloxy phenyl)-5, 7-di-t-butyl benzo furans-2-ketone, 3-(3, 4-3,5-dimethylphenyl)-5, 7-di-t-butyl benzo furans-2-ketone, 3-(2, 3-3,5-dimethylphenyl)-5, 7-di-t-butyl benzo furans-2-ketone.

15. fillers or toughener, comprising: such as with the glass roving of the glass fibre of fiberglass woven cloth form existence, glassmat or long filament, short glass fiber, granulated glass sphere and wollastonite.Glass fibre not only can short glass fiber but also can the form of continuous fibre (rove) be incorporated to.

16. static inhibitor, such as: sulfonamide derivatives is as N, the carboxyl ester of two (the hydroxyalkyl)-alkylamine of N-or-alkyl enamine, macrogol ester and ether, ethoxylation and carboxylic acid amides and glyceryl monostearate and distearin, and composition thereof.

17. biocides can be sterilant or antiseptic-germicide.

The amount of the compound of at least one formula I is 0.001 to 5 % by weight, preferably 0.01 to 3 % by weight, such as 0.001 to 3%, 0.01 to 2%, 0.01 to 1.5% or 0.025 to 1%, and relative to the weighing scale of polyamide resin.

Formula (I) Compound Phase is preferably 1:100 to 100:1, such as 1:90 to 90:1,1:80 to 80:1,1:70 to 70:1,1:60 to 60:1,1:50 to 50:1,1:40 to 40:1,1:30 to 30:1,1:20 to 20:1,1:10 to 10:1,1:5 to 5:1,1:4 to 4:1,1:3 to 3:1,1:2 to 2:1 or 1:1 for the weight ratio of the component (if present) of optional foregoing description.

According to the present invention, a kind of method of at least one solid-state material characteristic for improvement of polyamide resin is provided, said method comprising the steps of:

A) a kind of polymeric amide is provided;

B) carbamide compound of at least one formula I as above is provided; And

C) carbamide compound of formula I is included in polymeric amide.

Polymeric amide is preferably selected from aliphatic polyamide homopolymer, aliphatic polyamide copolymers, partially aromatic polymeric amide and mixture as above.Polyamide resin can comprise other components as above or additive as tinting material, antioxidant, uv-absorbing agent, photostabilizer, strongthener, filler, antifogging agent, releasing agent, biocide, static inhibitor and rheology modifier.In the carbamide compound of formula I, radicals R ¹, R ², Z and index x preferably has one of preferred implication.The amount of the carbamide compound of formula I can be 0.001 to 5 % by weight, and preferably 0.01 to 3 % by weight, more preferably 0.05 to 2 % by weight, relative to the weighing scale of polyamide resin.

By method of the present invention, polyamide resin has the solid-state properties of improvement.Especially, the solid-state properties being selected from mechanical characteristics and gloss is improved.Polyamide resin prepared according to the methods of the invention has tensile properties and the notched Izod impact toughness of improvement.Tensile properties is preferably selected from yielding stress, yield strain, break-draw strain, tensile stress at break, Young's modulus and shearing modulus.

At least one formula I and optional other component can be added to polyamide resin individually or after being mixed with each other.Optionally, each additive can such as be mixed with each other including in before polyamide polymer in melt (melt blended material).

Formula I is included in optional the including in polyamide resin of component to polyamide resin and this routine and can be undertaken by known method.Described including in can such as by being dry mixed, by the extruding of the mixture of various component, by conventional Masterbatch technology, add additivated polycondensate, to add the filler of additive as mixed in polymeric carrier etc. and carry out.

Described including in can be carried out in any heatable container (such as airtight equipment is as the container of kneader, mixing machine or stirring) being configured with agitator.The processing instance of composition of the present invention is: injection blow molding is shaping, extrude, blow molding, extrusion and blow molding, rotational moulding, in-mold decoration (injecting afterwards), slush molding, injection moulding, injection moulding altogether, shaping, compression moulding, compacting, film extrude (casting film; Blown film), fiber sprinning (fabric, non-woven), draw and mould (single shaft, twin shaft), annealing, deep-draw, calendering, mechanical deformation, sintering, coextrusion.According to known in the literature method, described in include in and preferably carry out in forcing machine or kneader.

It is inessential whether processing is carried out under inert atmosphere or oxygen exist.

The polyamide resin comprising formula I can use any suitable melt processing as injection moulding, extrudes, blowing, injection blow molding are shaping, hot-forming etc. and be formed as moulded products.Comprise polyamide resin normally film, fiber, sheet, pipe, work in-process, particle, container, blow-molded article or the monofilament of formula I.Described film can be unitary film or multilayer film or fiber.

Comprise the polyamide article of formula I, there is high strength, high rigidity, high notched Izod impact toughness, the strain of excellent break-draw, excellent tensile stress at break, the Young's modulus of excellence and the shearing modulus of excellence, this is in industries such as optics, automobile, aircraft, electrical/electronic, Sport & Casual, mechanical engineerings, or in the application in corrosive medium field particularly important.

Be not limited to aforesaid general introduction, the goods formed by the polyamide resin comprising formula I can comprise and have toughness, good dimensional stability at high temperature and the mechanical part of low tensile stress at break and shell, as gear, shell is as filter housing or solenoid valve casing, current heater, trailing cable, electric insulation part, the viewing window of storage tank or liquid storing pool (such as fuel and/or oil), lid, spectacle frame, ophthalmic lens, the camera lens of technical equipment, the viewing glass of heating process, the filtering cup of processing drinking water, bottle, gas or liquid meter, clock shell, watch case, motor car accessories, lampshade, lamp reflecting tablets, BLS, surgical material, the decoration of magnetictape cartridge or sports goods, or wrapping material.

Surface gloss is tested (test angles is 20 ° and 60 °) according to DIN 67530.Yielding stress, yield strain, tensile stress at break, break-draw strain and Young's modulus are tested according to EN ISO 527-2.But shellfish (Charpy) notched Izod impact toughness measures according to DIN EN ISO 179-2, at 23 DEG C, and pouring-in S shaped incision.Storage modulus G' and out-of-phase modulus G " is measure at temperature range is 15.1 DEG C to 197.3 DEG C according to ISO 6721-7.

Present the present invention will be illustrated in further detail by the following examples.But the following examples are only indicative and should not be considered as limitation of the present invention.

The preparation of formula I:

I.1 formula I, x=1 in formula, and R ¹=R ²

Embodiment 1:1,1'-(anti-form-1,4-cyclohexylidene) two (3-(tertiary butyl) urea)

Under an inert atmosphere, by isocyanic acid tertiary butyl ester (3.90g, anhydrous tetrahydro furan (THF) (50mL) solution 0.039mol) is slowly added to anti-form-1, in anhydrous THF (100mL) solution of 4-diamino cyclohexanediamine (2.10g, 0.019mol).Gained mixture is heated to reflux and stirs 24h.Throw out is filtered and washs with other anhydrous THF.Gained white solid recrystallization from DMF (DMF) is also dry under a high vacuum.

MS(70eV)：312(M ⁺)

Embodiment 2:1,1'-(anti-form-1,4-cyclohexylidene) two (3-(cyclohexyl) urea)

Under an inert atmosphere, by NSC 87419 (5.49g, anhydrous THF (50mL) solution 0.044mol) is slowly added to anti-form-1, in anhydrous THF (100mL) solution of 4-diamino cyclohexanediamine (2.51g, 0.022mol).Gained mixture is heated to reflux and stirs 24h.Throw out is filtered and washs with other anhydrous THF.Gained white solid recrystallization from DMF is also dry under a high vacuum.

MS(70eV)：364(M ⁺)

Embodiment 3:1,1'-(anti-form-1,4-cyclohexylidene) two (3-(sec.-propyl) urea)

Under an inert atmosphere, by Isopropylamine (1.25g, anhydrous THF (50mL) solution 0.022mol) is slowly added in anhydrous THF (100mL) solution of CHDI (1.75g, 0.011mol).Gained mixture is heated to reflux and stirs 24h.Throw out is filtered and washs with other anhydrous THF.Gained white solid recrystallization from DMF is also dry under a high vacuum.

MS(70eV)：284(M ⁺)

Embodiment 4:1,1'-(anti-form-1,4-cyclohexylidene) two (3-(1-ethyl propyl) urea)

Under an inert atmosphere, by 3-aminopentane (2.20g, anhydrous THF (50mL) solution 0.025mol) is slowly added in anhydrous THF (100mL) solution of CHDI (2.00g, 0.012mol).Gained mixture is heated to reflux and stirs 24h.Throw out is filtered and washs with other anhydrous THF.Gained white solid recrystallization from DMF is also dry under a high vacuum.

MS(70eV)：340(M ⁺)

Embodiment 5:1,1'-(cis-Isosorbide-5-Nitrae-cyclohexylidene) two (3-(cyclohexyl) urea)

Under an inert atmosphere, by isocyanato hexanaphthene (3.25g, anhydrous THF (50mL) solution 0.026mol) is slowly added in anhydrous THF (100mL) solution of cis-Isosorbide-5-Nitrae-cyclohexanediamine (1.50g, 0.013mol).Gained mixture is heated to reflux and stirs 24h.Throw out is filtered and washs with other anhydrous THF.Gained white solid recrystallization from MeOH is also dry under a high vacuum.

Fusing point: 252 DEG C

MS(70eV)：364(M ⁺)

Embodiment 6:1,1'-(cis-Isosorbide-5-Nitrae-cyclohexylidene) two (3-(tertiary butyl) urea)

Under an inert atmosphere, by tert-butyl isocyanate (2.57g, anhydrous THF (50mL) solution 0.026mol) is slowly added in anhydrous THF (100mL) solution of cis-Isosorbide-5-Nitrae-cyclohexanediamine (1.50g, 0.013mol).Gained mixture is heated to reflux and stirs 24h.Throw out is filtered and washs with other anhydrous THF.Gained white solid recrystallization from MeOH is also dry under a high vacuum.

Fusing point: 319 DEG C

MS(70eV)：312(M ⁺)

The compound of embodiment 7 to 13 is prepared in a similar fashion.

Embodiment 7:1,1'-(anti-form-1,4-cyclohexylidene) two (3-(1,1-dimethyl propyl) urea)

MS(70eV)：340(M ⁺)

Embodiment 8:1,1'-(anti-form-1,4-cyclohexylidene) two (3-(tertiary octyl group) urea)

MS(70eV)：426(M ⁺)

Embodiment 9:1,1'-(anti-form-1,4-cyclohexylidene) two (3-(1,5-dimethylhexanyl) urea)

MS(70eV)：425(M ⁺)

Embodiment 10:1,1'-(anti-form-1,4-cyclohexylidene) two (3-(1-adamantyl) urea)

MS(70eV)：468(M ⁺)

Embodiment 11:1,1'-(anti-form-1,4-cyclohexylidene) two (3-normal-butyl urea)

Fusing point: 358 DEG C

MS(70eV)：312(M ⁺)

Embodiment 12:1,1'-(anti-form-1,4-cyclohexylidene) two (3-(n-propyl) urea)

MS(70eV)：284(M ⁺)

Embodiment 13:1,1'-(anti-form-1,4-cyclohexylidene) two (3-(ethyl) urea)

MS(70eV)：256(M ⁺)

Embodiment 14:(4-urea groups cyclohexyl) urea

By anti-form-1,4-diamino-cyclohexane (2.10g, 0.019mol) is dissolved in water (40mL).By adding HCl, solution is adjusted to pH5-7.Under agitation the potassium cyanate of 3.30g is slowly added.Gained mixture is heated to reflux and stirs 24h.Throw out to be filtered and with other water washing.The white solid of gained is dry under a high vacuum.

I.2 the compound of formula I, wherein x=1, and R ¹be different from R ².

The embodiment 15:1-tertiary butyl-3-[4-(cyclohexyl carbamyl is amino) cyclohexyl] urea

15.1 anti-form-1s-(4-aminocyclohexyl)-3-cyclohexyl urea

Under an inert atmosphere, by anti-form-1, anhydrous THF (500mL) solution of 4-diamino-cyclohexane (6.15g, 0.054mol) is cooled to-40 DEG C in cooling bath (Virahol/dry ice).With vigorous stirring, anhydrous THF (100mL) solution of isocyanato hexanaphthene (6.75g, 0.054mol) is slowly added.Gained mixture is at room temperature stirred 24h again.The white solid of precipitation is filtered, and to be suspended in water, and to be acidified to pH be 2 (HCl).Again filter the clear solution of formation, and make the pH of filtrate be 8 (NaOH), thus anti-form-1-(4-aminocyclohexyl)-3-cyclohexyl urea precipitates as white solid.

The 15.21-tertiary butyl-3-[4-(cyclohexyl carbamyl is amino) cyclohexyl] urea

Under an inert atmosphere, by isocyanic acid tertiary butyl ester (1.17g, the solution (50mL) of anhydrous N-methyl-2-Pyrrolidone (NMP) 0.012mol) is slowly added in the anhydrous nmp solution (100mL) of anti-form-1-(4-aminocyclohexyl)-3-cyclohexyl urea (2.83g, 0.012mol).Gained mixture is heated to 70 DEG C and stirs 24h.Described solution precipitates and filters in 1M HCl.Wash gained white solid with THF, and from DMF recrystallization and dry under a high vacuum.

Fusing point: 325 DEG C

MS(70eV)：338(M ⁺)

I.3 formula I, x=2 in formula and R ¹=R ²

Embodiment 16:

16.1 anti-form-1s-(4-aminocyclohexyl)-3-cyclohexyl urea

Under an argon atmosphere, by anti-form-1,4-diamino-cyclohexane (6.15g, 0.054mmol) to be added in flame-dried Schlenk bottle and to be dissolved in THF (500mL).Gained solution is cooled to-40 DEG C in cooling bath (Virahol/dry ice), and the cyclohexyl isocyanate (6.75g, 0.054mmol) that will be diluted in THF (100mL) slowly adds with vigorous stirring.Reaction mixture is at room temperature stirred 12h.Filtered by the white solid of precipitation, suspend in water, being acidified to pH is 2 (HCl).Again filter the clear solution of formation, and make the pH of filtrate be 8 (NaOH), thus anti-form-1-(4-aminocyclohexyl)-3-cyclohexyl urea precipitates as white solid.

16.2

The solution of the THF of anti-form-1-(4-aminocyclohexyl)-3-cyclohexyl urea is loaded in flask, and blasts phosgene wherein.After having reacted, under reduced pressure remove excessive phosgene and solvent and obtain titled reference compound.

I.4 formula I, x=3 in formula and R ¹=R ²

Embodiment 17

Under an argon atmosphere, anti-form-1-(4-aminocyclohexyl)-3-cyclohexyl urea (3.2g, 13mmol) to be added in flame-dried Schlenk bottle and to be dissolved in NMP.The CHDI (1g, 6mmol) be diluted in NMP is slowly added with vigorous stirring.Gained mixture is heated to 80 DEG C and stirs 12h.Described solution precipitates and filters in 1M HCl.The white solid of gained is washed with THF, and dry 2h (70 DEG C, 100 millibars) under vacuo.

MS(70eV)：265(M ⁺)

Unless otherwise noted, in the embodiment of operation, following conventional steps is used.

Mixing step:

Precise concentration is the polyamide granules of 1.0 % by weight and the carbamide compound of formula I.Then component is carried out drum-type mixing.Then be 300rpm by said mixture at rotating speed, melt temperature is blended in the common spiral biaxial screw mixing machine (ZSK18) of 260 DEG C and turnout is 6kg per hour.Process pure polymeric amide in a like fashion to prepare the sample of blank.

Use polymeric amide below:

-be purchased from German BASF SE's b27:PA 6 grade

Injection moulding:

Be 30mm at screw diameter, melt temperature is carry out injection moulding in the injection moulding machine of 260 DEG C.At mould-cavity temperature is 80 DEG C, melts is injected in die cavity.Dwell pressure is 600 bar.The test sample of preparation is the standard tensile batten according to DIN EN standard 527-2, Typ 1A and the but shellfish batten according to ISO 179-2/1eA (F).

The composition containing formula I listed in the following Table I of preparation described above, reference group compound and Comparative composition, sample thickness is set as 4.0mm.

Table I

* N, N`-hexane-1,6-bis-base two [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amide], CAS 23128-74-7

* Ceasit AV, powder flow aid, purchased from Baerlocher

The IC present composition

CC Comparative composition

Table II: optical characteristics selected by the composition containing formula I, reference group compound and Comparative composition

When compared with not having the composition of adding type I, formula I is used to improve the gloss of the daiamid composition mixing described formula I.

Table III: comprise the composition of formula I, reference group compound and Comparative composition tensile properties

?	Yielding stress	Tensile stress at break	Yield strain	Break-draw strains	Yang type modulus
						?	[MPa]	[MPa]	[％]	[％]	[MPa]
Object of reference	80.43	47.67	4.08	21.87	3013
						IC?1	88.31	55.28	3.88	14.38	3255
IC?2	89.84	50.71	3.95	12.43	3251
						CC?1	88.58	54.7	3.79	9.91	3224
CC2	91.34	75.92	3.79	8.01	3614
						CC3	93.38	77.86	3.76	7.98	3690

When compared with there is no the composition of adding type I, the numerical value using formula I to increase Young's modulus (Young's modulus) and break-draw to strain.

Table IV: the but shellfish notched Izod impact toughness of the composition containing formula I, reference group compound and Comparative composition

When compared with the composition not having the composition of adding type I or add talcum, the Amilan polyamide resin composition comprising formula I demonstrates excellent notched Izod impact toughness 23 DEG C time.Test thickness of sample is 4mm.

DMTA-tests

Dynamic mechanical analysis (carrying out DMTA test according to ISO 6721-7) is adopted to test storage modulus G` (elastic response modulus) and out-of-phase modulus G`` (viscous response modulus).The sample of drying regime is adopted to test in RDA 1 rheometer.Test sample is of a size of long 4.0cm, wide 1.0cm, thick 0.1cm (being made up of pressing plate).The strain applied during beginning: 0.2%, frequency 1Hz, the starting temperature heated in a nitrogen atmosphere is 15.1 DEG C (temperature amplitudes: 5K).By pre-treatment at sample under vacuum 80 DEG C 3 days before test.

Table V: the storage modulus G` of the composition containing formula I and reference group compound and out-of-phase modulus G``

The pure polymeric amide (dry) tested by DMTA and the second-order transition temperature of composition I C1 (dry) are 64 DEG C.As can be seen from storage modulus and out-of-phase modulus, higher than T _gtime, the change of IC1 rigidity is less than the stiffness change of reference group compound.Therefore, in the temperature range higher than above-mentioned second-order transition temperature the rigidity of IC1 higher than the rigidity of reference group compound.

Claims

1. the purposes of the carbamide compound of at least one formula I, for improvement of at least one solid-state properties of polyamide resin

Wherein

X is 1,2 or 3;

Z is selected from C ₃-C ₁₀-alkane two base, unsubstituted or the arylidene be substituted, the unsubstituted or arylidene-C that is substituted ₁-C ₄-alkylene-arylene, unsubstituted or the inferior heteroaryl be substituted, the unsubstituted or inferior heteroaryl-C that is substituted ₁-C ₄-alkylidene group-inferior heteroaryl, the unsubstituted or C that is substituted ₅-C ₈-cycloalkylidene, the unsubstituted or C that is substituted ₅-C ₈-cycloalkylidene-C ₁-C ₄-alkylidene group-C ₅-C ₈-cycloalkylidene, the unsubstituted or sub-Heterocyclylalkyl that is substituted and sub-Heterocyclylalkyl-C that is unsubstituted or that be substituted ₁-C ₄-alkylidene group-Ya Heterocyclylalkyl.

2. the purposes of claim 1, wherein solid-state properties is selected from mechanical characteristics and gloss.

3. the purposes of claim 2, wherein mechanical characteristics is selected from tensile properties and notched Izod impact toughness.

4. the purposes of claim 3, wherein tensile properties is selected from yielding stress, yield strain, break-draw strain, tensile stress at break, Young's modulus and shearing modulus.

5. the purposes of claim 1, wherein R ¹and R ²be independently from each other straight chain C ₁-C ₇-alkyl, side chain C ₃-C ₁₀-alkyl, the unsubstituted or C that is substituted ₃-C ₁₂-cycloalkyl, the unsubstituted or C that is substituted ₃-C ₁₂-cycloalkyl-C ₁-C ₄-alkyl, the unsubstituted or aryl that is substituted and aryl-C that is unsubstituted or that be substituted ₁-C ₄-alkyl.

6. the purposes any one of the claims, R in its Chinese style I ¹and R ²be independently from each other hydrogen, side chain C ₃-C ₁₀-alkyl, C ₅-C ₁₂-cycloalkyl, C ₅-C ₁₂-cycloalkyl-C ₁-C ₄-alkyl, phenyl and phenyl-C ₁-C ₄-alkyl, each ring of the 4 kinds of groups wherein finally mentioned is unsubstituted or by one or more identical or different radicals R ^areplaced, wherein R ^abe selected from C ₁-C ₁₀-alkyl or halogen.

7. the purposes any one of the claims, R in its Chinese style I ¹and R ²be independently from each other hydrogen; Side chain C ₃-C ₁₀-alkyl, its secondary carbon(atom) by alkyl or tertiary carbon atom and be connected on skeleton; Unsubstituted or by 1 or 2 radicals R ^athe C replaced ₅-C ₁₀-cycloalkyl; With unsubstituted or by 1 or 2 radicals R ^athe phenyl replaced.

8. the purposes any one of the claims, R in its Chinese style I ¹and R ²there is identical implication.

9. the purposes any one of the claims, in its Chinese style I, Z is C ₅-C ₈-alkylidene group, C ₅-C ₇-cycloalkylidene, C ₅-C ₇-cycloalkylidene-CH ₂-C ₅-C ₇-cycloalkylidene, phenylene or phenylene-CH ₂-phenylene, each ring of the 4 kinds of groups wherein finally mentioned is unsubstituted or by one or two identical or different radicals R ^breplaced, wherein R ^bbe selected from C ₁-C ₁₀-alkyl and halogen.

10. the purposes of claim 9, in its Chinese style I, Z is straight chain C ₅-C ₈-alkylidene group or C ₅-C ₇-cycloalkylidene.

Purposes any one of 11. the claims, in its Chinese style I, x is 1.

Purposes any one of 12. the claims, in its Chinese style I

R ¹and R ²be identical and be selected from hydrogen, the tertiary butyl, 1,1-dimethyl propyl, 1,5-dimethylhexanyl, 1,1,3,3-tetramethyl butyl and 1-adamantyl;

Z is trans Isosorbide-5-Nitrae-cyclohexylidene; And

X is 1.

Purposes any one of 13. the claims, wherein polyamide resin is selected from aliphatic polyamide homopolymer, aliphatic polyamide copolymers, partially aromatic polymeric amide and composition thereof.

Purposes any one of 14. the claims, wherein polyamide polymer is selected from PA 6, PA 7, PA 10, PA 11, PA 12, PA 66, PA 69, PA 610, PA 612, PA 1010, PA 6/66, PA 66/6, PA 66/610 and composition thereof, is preferably selected from PA 6, PA 11, PA12, PA 66, PA 610, PA 66/6 and PA 6/66.

The purposes of 15. claims 14, wherein polyamide polymer is selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66 and in formula I, R ¹and R ²be identical and be selected from hydrogen, the tertiary butyl, 1,1-dimethyl propyl, 1,5-dimethylhexanyl, 1,1,3,3-tetramethyl butyl and 1-adamantyl; Z is trans Isosorbide-5-Nitrae-cyclohexylidene; And x is 1.

Purposes any one of 16. the claims, wherein polyamide resin comprises the amount of formula I is 0.001 to 5 % by weight, preferably 0.01 to 3 % by weight, more preferably 0.05 to 2 % by weight, relative to the weighing scale of fluoropolymer resin.

Purposes any one of 17. the claims, wherein polyamide resin also comprise at least one other be selected from following additive: tinting material, antioxidant, uv-absorbing agent, photostabilizer, strongthener, filler, antifogging agent, releasing agent, biocide, static inhibitor and rheology modifier.

18. 1 kinds of methods improving at least one solid-state material characteristic of polyamide resin, described method comprise by least one any one of claim 1 and 5 to 12 the carbamide compound of formula I that limits be added to polyamide resin.