CN104058989B - A star polyamide-ester-terminated polyhydric alcohol ester compound - Google Patents

A star polyamide-ester-terminated polyhydric alcohol ester compound Download PDF

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CN104058989B
CN104058989B CN 201410217922 CN201410217922A CN104058989B CN 104058989 B CN104058989 B CN 104058989B CN 201410217922 CN201410217922 CN 201410217922 CN 201410217922 A CN201410217922 A CN 201410217922A CN 104058989 B CN104058989 B CN 104058989B
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白桦
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江南大学
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Abstract

本发明公开了一种星形酯封端聚酰胺多元醇酯化合物,属于化工技术领域。 The present invention discloses a star polyol ester-terminated polyamide ester compound, belonging to the field of chemical technology. 本发明涉及一种星形酯封端聚酰胺多元醇酯化合物、其制备方法及应用,该类化合物在低极性溶剂中具有优良的凝胶性能,因而在油酯类凝胶化制品方面有良好的应用前景。 The present invention relates to a star polyol ester-terminated polyamide ester compounds, their preparation and use, these compounds have excellent gel properties in low-polarity solvents, and therefore there is in the gelled oil-based products good prospect.

Description

一种星形酯封端聚酿胺多元醇酯化合物 A star stuffed amine-terminated poly ester polyol compound

技术领域 FIELD

[0001] 本发明一种星形酯封端聚酰胺多元醇酯化合物,具体涉及一种星形酯封端聚酰胺多元醇酯化合物、其制备方法及应用,该类化合物在低极性溶剂中具有优良的凝胶性能,因而在油酯类凝胶化制品方面有良好的应用前景,属于化工技术领域。 [0001] The present invention is a star polyamide-ester-terminated polyhydric alcohol ester compound, particularly relates to a star polyol ester-terminated polyamide ester compounds, their preparation and application of these compounds in a low polar solvent gel having excellent properties, which has good application prospect in the gelled oil-based products, belonging to the field of chemical technology.

背景技术 Background technique

[0002] 有机凝胶剂能够与低极性溶剂通过分子间的氢键、范德华力相互作用,在溶剂内自组装成三维网络结构,从而使数倍乃至数千倍于自身分子个数的溶剂被包裹在这种网络结构中,形成热可逆的有机凝胶。 [0002] The organic gelling agent and a low polar solvent capable of hydrogen bonding by intermolecular van der Waals interactions, in a solvent self-assemble into a three-dimensional network structure, so that even several thousands of times the number of molecules in the solvent itself wrapped in such a network configuration, a thermoreversible organogel is formed. 有机凝胶由于兼有固体与液体的特殊性质,使产品具有合适的粘稠度或出众的透明视觉效果,赋予了产品较高的品质和商业价值,被广泛应用于个人护理品、家居用品、蜡烛制品等行业。 Organic gel due to the special nature of both solid and liquid, the product has the right consistency or superior transparent visual effect, given the high product quality and commercial value, it is widely used in personal care products, household goods, candle products industries. 其中商业化的以二聚酸为基础原料的US5783657、CN1238678、US2002068811等专利公开的具有通式(6)、(7)线形分子结构的酯封端聚酰胺凝胶剂及叔胺封端聚酰胺凝胶剂具有优良的凝胶性能,有较好的发展潜力。 Wherein the ester-terminated polyamide gels and tertiary amine end capped commercial dimeric acid based raw materials US5783657, CN1238678, US2002068811 other patent disclosed having the general formula (6) (7) linear molecular structure of polyamide gel gel with excellent performance, has good potential for development.

Figure CN104058989BD00051

[0005] 式(7) [0005] Formula (7)

[0006] 但对于线性结构聚酰胺凝胶剂来说,一方面随着分子中酰胺基团增加,分子间作用力越强,形成的凝胶相强度越高,对凝胶相的形成有利。 [0006] But for the polyamide gelling agent is a linear structure, on the one hand with the amide groups in the molecule increases, the stronger the intermolecular force, the higher the strength of the formed gel phase, it is advantageous to form a gel phase. 另一方面分子中酰胺基团增加, 凝胶剂分子极性相对增大,与低极性溶剂相容性将变差,反过来又影响凝胶相的稳定。 On the other hand an amide group in the molecule increases, the gelling agent is increased relative molecular polarity, the compatibility with the low polar solvent will deteriorate, which in turn affect the stability of the gel phase. 现有的解决方案一般是通过以长碳链脂肪醇或长碳链仲胺为封端剂,将其与二聚酸、二胺共聚, 形成酯封端聚酰胺或叔胺封端聚酰胺凝胶剂,封端剂碳链越长,凝胶相往往越稳定。 Existing solutions typically terminated by an ester-terminated polyamide or the polyamide tertiary amine condensing a long carbon chain fatty alcohols or long chain secondary amine capping agent, which is copolymerized with the dimer acid, diamine, formed the longer the glue, the carbon chain capping agent, often more stable gel phase. 但当脂肪醇或脂肪胺的碳链大于二十二个碳后,该脂肪醇或胺将越来越昂贵和稀少,产品成本会因此急剧增加。 But when fatty alcohols or fatty amines over 21 carbon chain two carbons, which aliphatic alcohol or amine increasingly scarce and expensive, and therefore will dramatically increase the cost of the product. 因此通过分子设计,用更廉价、简便的方法对现有凝胶剂分子结构进一步改进,进一步增加凝胶分子中酯基、封端剂烃基的数量,在保持凝胶剂凝胶能力的同时,进一步降低分子极性,为解决上述问题提供理论和实践的支持,对进一步降低凝胶制品制造成本有重要的现实意义。 Therefore, by molecular design, a more inexpensive and simple method for the gel prior to further improve the molecular structure, further increasing the number of gels in the molecule an ester group, a hydrocarbon group capping agent, while maintaining the ability to gel the gelling agent, decrease of the molecular polarity, to provide support for the theory and practice to solve the above problems, there are important practical significance to further reduce manufacturing costs gel products.

发明内容 SUMMARY

[0007] 本发明提供了一种星形酯封端聚酰胺多元醇酯化合物及其制备方法和用途。 [0007] The present invention provides a star polyol ester-terminated polyamide ester compounds, preparation method and uses.

[0008] 本发明通过如下技术方案实现: [0008] The present invention is achieved by the following technical solutions:

[0009] -种星形酯封端聚酰胺多元醇酯化合物,该化合物结构如通式(1)所示: [0009] - star species capped polyamic ester polyol ester compounds, such as compounds of the general formula (1):

[0010] [0010]

Figure CN104058989BD00061

[0011] 式(1) [0011] Formula (1)

[0012] 其中, [0012] wherein,

[0013] RT是通式为RT(0H)T的多元醇中除了羟基以外的含有至少3个碳原子和任意性的含有或不含一个或多个氧原子的有机基团,氧原子数量在〇~20之间; [0013] RT polyhydric alcohol of the general formula RT (0H) T in addition to the hydroxyl group containing at least 3 carbon atoms and optionally containing one or more free or oxygen atom, an organic group, the number of oxygen atoms ~ 20 billion;

[0014]T表示通式为RT(OH)T的多元醇所含羟基的数量,T=3或4; [0014] T represents the formula RT (OH) T is the number of hydroxyl groups contained in the polyol, T = 3 or 4;

[0015]R1是C4-C24的烃基,优选C12-C18的烃基; [0015] R1 is a hydrocarbon group of C4-C24, preferably C12-C18 hydrocarbon group;

[0016]R2是C4-C42的烃基,优选C6-C36的烃基; [0016] R2 is C4-C42 hydrocarbyl, preferably C6-C36 hydrocarbon group;

[0017]R3是C2-C12的烃基,优选C2-C6的烃基 [0017] R3 is C2-C12 hydrocarbon group, preferably a C2-C6 hydrocarbon group

[0018]R4是C1-C23的烃基,优选C11-C17的烃基; [0018] R4 is C1-C23 hydrocarbon group, preferably a C11-C17 hydrocarbon group;

[0019]n表示各支链中重复单元的数量,各支链间的n值可以相等也可不等,可以为0但不全部为0,且数值为0~3,优选0~2; [0019] n represents the number of repeating units in each chain, branched, n is a value between the respective branches and the like may not be equal, but not all may be 0 0, and a value of 0 to 3, preferably 0 to 2;

[0020] x表示化合物中具有通式(2)分子结构支链的数量,2 <x< 4 ; [0020] x represents the compound having the general formula (2) the number of molecules of a branched structure, 2 <x <4;

[0021] [0021]

Figure CN104058989BD00062

[0022] 式⑵ [0022] Formula ⑵

[0023] y表示化合物中具有通式(3)分子结构支链的数量,0 <y< 2 ;x+y=3或4 ; [0023] y represents the number of a compound having the general formula (3) branched molecular structure, 0 <y <2; x + y = 3 or 4;

[0024] [0024]

Figure CN104058989BD00063

[0025] 式⑶ [0025] Formula ⑶

[0026] x+y=T〇 [0026] x + y = T〇

[0027] 根据本发明,酯封端聚酰胺多元醇酯分子结构中至少含三条以上由酯键相连的支链,其中至少2条支链是具有通式(2)分子结构的支链,整个分子呈星形结构。 [0027] According to the present invention, the ester-terminated polyamide molecular structure of polyol esters containing at least three or more branched-chain linked by a ester bond, wherein at least two branches are branched chain having the general formula (2) molecular structure, the entire star-shaped molecular structure.

[0028] 所述通式为RT(0H)T的多元醇是:丙三醇、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷、季戊四醇。 [0028] The formula RT (0H) T polyols are: glycerol, trimethylol methane, trimethylol ethane, trimethylol propane, pentaerythritol.

[0029] 其中优选的酯封端聚酰胺多元醇酯分子结构为: [0029] Among the preferred ester polyol ester-terminated polyamide molecular structure:

[0030] [0030]

Figure CN104058989BD00071

[0031]式(8) [0031] Formula (8)

[0032] 单脂肪酸双酯封端聚酰胺甘油酯 [0032] bis mono fatty acid glyceride ester-terminated polyamide

[0033] [0033]

Figure CN104058989BD00072

[0040]式(11) [0040] Formula (11)

[0041] 三酯封端聚酰胺三羟甲基乙烷酯 [0041] The three ester-terminated polyamide trimethylolethane ester

[0042] [0042]

Figure CN104058989BD00081

[0052]式(15) [0052] Formula (15)

[0053] 单脂肪酸三酯封端聚酰胺季戊四醇酯 [0053] mono fatty acid triester of pentaerythritol ester-terminated polyamide

[0054] [0054]

Figure CN104058989BD00091

[0055]式(16) [0055] Formula (16)

[0056] 双脂肪酸双酯封端聚酰胺季戊四醇酯 [0056] bis-bis fatty acid esters of pentaerythritol ester-terminated polyamide

[0057] 其中n、Rl、R2、R3、R4变量如前文所述。 [0057] wherein n, Rl, R2, R3, R4 variables are as previously described.

[0058] 本发明提供了一种星形酯封端聚酰胺多元醇酯化合物的制备方法,其关键在于反应分步进行,每一步反应都采用已知成熟技术,保证了每步反应都只生成所需结构的化合物,最后得到具有确定分子结构的产品。 [0058] The present invention provides a method of preparing star-terminated polyamide polyol ester compound, which is critical that the reaction stepwise, each step mature technology using known reactions, each reaction step only to ensure the generation the structure of the desired compound, to obtain the final product with a defined molecular structure. 具体合成方法包括如下步骤: Specific synthesis method comprising the steps of:

[0059]步骤⑴一端为羧基的单酯封端聚酰胺的制备 Preparation [0059] Step ⑴ one end carboxyl group-terminated polyamide monoester

[0060] 按反应方程I将二元酸、二元胺、一元醇以一定摩尔比混合在通氮保护的情况下, 混合反应制得一端为羧基的单酯封端聚酰胺。 [0060] Reaction Equation I will diacids, diamines, monohydric alcohol in a molar ratio of nitrogen in the case of through-mixing reaction of carboxy end-terminated polyamide monoesters.

[0061] [0061]

Figure CN104058989BD00092

[0062]方程I [0062] Equation I

[0063] 根据本发明,方程I中产物单酯封端聚酰胺根据反应物投料比的不同可以得到重复单元数固定的一种单酯封端聚酰胺或是几种具不同重复单元数的单酯封端聚酰胺混合物,例如,当二元酸:二元胺:一元醇=2 : 1 : 1(摩尔比)时,只能得到n=l-种单酯封端聚酰胺,当二元酸:二元胺:一元醇=3 : 2 : 1 (摩尔比)时,只能得到n=2-种单酯封端聚酰胺,但当二元酸:二元胺:一元醇=9 : 5 : 4 (摩尔比)时,却可以得到n=l和n=2两种单酯封端聚酰胺的混合物,并可计算出n=l与n=2两种单酯封端聚酰胺的摩尔比为3 : 1,当二元酸:二元胺:一元醇=7 : 4 : 1 (摩尔比)时,却可以得到n=l和n=0两种单酯封端聚酰胺的混合物,并可计算出n=l与n=0两种单酯封端聚酰胺的摩尔比为3 : 1,其中n=0的单酯封端聚酰胺作为一种特别的重复单元数为0的单酯封端聚酰胺是聚酰胺聚合度为〇的极 [0063] According to the invention, the products of equation I monoester terminated polyamide can be a fixed number of repeating units one monoester or mono-terminated polyamide having several different repeating units in accordance with various reactant feed ratio ester-terminated polyamide blend, for example, when a diacid: diamine: monohydric alcohol = 2: 1: 1 (molar ratio), to give only a single species of n = l- ester-terminated polyamide, when two yuan acid: diamine: monohydric alcohol = 3: 2: 1 (molar ratio), to give only a single species of n = 2- ester-terminated polyamide, but diacid: diamine: monohydric alcohol = 9: 5: 4 (molar ratio), it can be a mixture of n = 2 the two single ester-terminated polyamide and n = l, n = l can be calculated with n = 2 the two single ester-terminated polyamide molar ratio of 3: 1, when a diacid: diamine: monohydric alcohol = 7: 4: 1 (molar ratio), but may be a mixture of n = l n = 0 and two single ester-terminated polyamide to give , with n = 0 and two single ester-terminated polyamide molar ratio of n = l is calculated as 3: 1, wherein n = 0 monoester terminated polyamide as a particular number of repeating units of 0 single ester-terminated polyamide is polyamide polymerization degree of square pole 形态,实际上是一种二元酸单酯,所形成支链也可称为二元酸单酯支链。 Form, is actually a dibasic acid monoester, the formed branched dibasic acids may also be referred to as a branched monoester.

[0064]根据本发明,方程I中具有H00C-R2-C00H结构的二元酸是二聚酸或是二聚酸与己二酸、庚二酸、辛二酸、壬二酸、癸二酸、i^一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸中的任意一种或几种的混合物,混合物中二聚酸摩尔含量大于50%,优选全部使用二聚酸或二聚酸摩尔含量大于80%的二元酸混合物。 [0064] According to the invention, a dibasic acid having the equation I H00C-R2-C00H structure is a dimer acid or dimer acid and adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid , i ^ a dodecanedioic acid, dodecanedioic acid, tridecanedioic acid, mixtures of any one or more of tetradecane diacid, dimer acid molar content of the mixture is greater than 50%, preferably all use dimer acid or dimer acid content of greater than 80 mole% of the dibasic acid mixture.

[0065] 根据本发明,方程I中具有H2N-R3-NH2结构的二元胺是乙二胺、1,2_丙二胺、 1,3-丙二胺、2, 2-二甲基-1,3-丙二胺、1,4- 丁二胺、1,5-戊二胺、2-甲基-1,5-戊二胺、 1,6-己二胺、环己二胺、1,7-庚二胺、1,8-辛二胺、1,9-壬二胺、癸二胺、十二烧二兀胺, 或是上述二元胺以任意比例混合组成的混合物;优选乙二胺、1,2-丙二胺、1,3-丙二胺、 1,4- 丁二胺、1,5-戊二胺、1,6-己二胺。 [0065] According to the present invention, having the equation I H2N-R3-NH2 diamines are ethylenediamine structure, 1,2_-propanediamine, 1,3-propanediamine, 2,2-dimethyl - 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, cyclohexanediamine, 1,7-heptane diamine, 1,8-octane diamine, 1,9-nonane diamine, decamethylene diamine, dodecamethylene burning two Wu amine, or the above-described diamine mixed in any proportion mixtures thereof; preferably ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine.

[0066] 根据本发明,方程I中n表示分子中重复单元的数目,n彡3,优选n彡2 ; [0066] According to the present invention, the equation I n represents the number of repeating units in the molecule, n San 3, preferably n San 2;

[0067] 步骤(2)星形酯封端聚酰胺多元醇酯的的制备: [0067] Preparation of Step (2) a star polyamide-ester-terminated polyol esters:

[0068] [0068]

Figure CN104058989BD00101

[0069] 按反应方程II或III,将多元醇或多元醇酯与步骤(1)制得的一端为羧基的单酯封端聚酰胺、一元酸、催化剂按一定比例混合进行酯化反应制得通式(1)结构的星形酯封端聚酰胺多元醇酯; [0069] Reaction Equation II or III, polyol esters or polyol in step (1) is a carboxyl group at one end obtained mono ester-terminated polyamide, a monobasic acid, by mixing a catalyst for esterification to give star ester (1) the structure of formula polyol ester-terminated polyamide;

[0070] 反应方程II [0070] Reaction Equation II

[0071] [0071]

[0072] 反应方程III [0072] Reaction Equation III

Figure CN104058989BD00102

[0073] 根据本发明,反应方程II、111中所用单酯封端聚酰胺可以是重复单元数n值固定的一种单酯封端聚酰胺,也可以是几种具有不同种重复单元数n值的单酯封端聚酰胺的混合物,反应得到通式(1)结构的星形酯封端聚酰胺多元醇酯各支链间的n值可以相等也可以不等,可以为〇但不全部为〇,当n值为0时,该支链本发明称其为n=0的单酯封端聚酰胺;也可根据其实际化学结构称其为二元酸单酯支链,例如,n=0的十八醇酯封端聚酰胺支链也可称为二元酸十八醇酯支链,具有不同n值的单酯封端聚酰胺的混合物与多元醇或多元醇酯反应,得到的也会是具有不同重复单元数酯封端聚酰胺支链的聚酰胺多元醇酯,但其分子结构仍只会是具有多条支链的星形结构。 [0073] According to the present invention, the reaction equation II, 111 as a single ester-terminated polyamide of repeating units n may be a fixed value of a single-ester-terminated polyamide, or may be of several different kinds of repeating units n single ester-terminated polyamide values ​​mixture, the reaction-terminated star general formula (1) a polyamide structure among n values ​​of branched polyol esters may equally be unequal, but may not be all square is square, when n is 0, the present invention is referred to as the branched n = 0 monoester terminated polyamide; also be based on its actual chemical structure referred to as a dibasic acid monoester branched chain, e.g., n = 0 octadecyl-terminated polyamide may also be referred to as a branched chain dibasic acid octadecyl branched chain, mono-terminated polyamide having different n values ​​with a polyol or mixture of polyol ester, to give also polyamide polyol ester having a different number of repeating units is ester-terminated polyamide branched, but it is still only a molecular structure having a plurality of star-branched structure.

[0074] 根据本发明,反应方程II中多元醇是丙三醇、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷、季戊四醇,优选丙三醇、三羟甲基甲烷、三羟甲基丙烷、季戊四醇。 [0074] According to the present invention, the reaction in equation II the polyol is glycerol, trimethylol methane, trimethylol ethane, trimethylol propane, pentaerythritol, preferably glycerol, trimethylol methane, trimethylol propane, pentaerythritol.

[0075] 根据本发明,反应方程III中的不饱和多元醇酯是上述多元醇的单酯或多酯,优选单酯。 [0075] According to the present invention, the unsaturated polyol ester is a reaction equation III ester of mono- or polyhydric alcohols, preferably monoesters.

[0076] 根据本发明,反应方程II中具有R4C00H结构的一元酸是正辛酸、正癸酸、十二酸、 十四酸、十六酸、十八酸、二十烷酸、二十二烷酸、二十四烷酸、二十八烷酸或是上述一元酸以任意比混合组成的混合物;优选十二酸、十四酸、十六酸、十八酸。 Monobasic acid [0076] According to the present invention, the reaction in equation II having R4C00H structure is n-octanoic, n-decanoic acid, dodecanoic acid, myristic acid, palmitic acid, stearic acid, eicosanoic acid, behenic acid , lignoceric acid, octacosanoic acid or a monobasic acid is a mixture consisting of a mixture in any ratio; preferably lauric acid, myristic acid, palmitic acid, stearic acid.

[0077] 根据本发明,反应方程II、111中催化剂为钛酸四丁酯、氯化亚锡、二月桂酸二丁基锡;优选钛酸四丁酯。 [0077] According to the present invention, the reaction equation II, 111 the catalyst is tetrabutyl titanate, stannous chloride, dibutyl tin dilaurate; preferably tetrabutyl titanate.

[0078] 本发明所提供的星形酯封端聚酰胺多元醇酯的制备方法,原料来源广泛,合成方法简单,易实施,化合物的核结构、支链数量、长度、种类均可调,相对于线形酯封端聚酰胺, 分子结构由一维变为二维或三维,可更方便改性以应用于个人护理品、家居用品、透明蜡烛等诸多领域。 Preparation Method [0078] The star-ester-terminated polyamide of the present invention provides a polyol ester, widely available raw materials, synthesis method is simple, easy to implement, the core structure of the compound, number of branches, the length, the type can be adjusted, relative ester-terminated polyamide to a linear, one-dimensional molecular structure becomes two or three dimensions, can be modified to be more convenient for personal care products, household goods, and many other areas transparent candle.

[0079] 本发明所述的星形酯封端聚酰胺多元醇酯作为凝胶剂可与低极性溶剂在低于溶剂沸点高于溶剂凝固点温度之间混合成均相,在室温或更低温度下冷却,形成有机凝胶,星形酯封端聚酰胺多元醇酯占有机凝胶总重的5%~90%,低极性溶剂是烃、矿物油、植物油、 动物油、脂肪酸甲酯、环氧脂肪酸甲酯,脂肪酸甘油酯、脂肪酸异丙酯中的一种或几种。 [0079] The star-ester-terminated polyamide of the present invention, a polyol ester as a gelling agent in a polar solvent with a low boiling point lower than the above are mixed into a homogeneous temperature between the freezing point of the solvent, at room temperature or lower cooling at a temperature to form an organic gel, ester-terminated polyamide star polyol ester occupies 5% to 90% of the total weight of the organogel, low-polarity solvent is a hydrocarbon, mineral oil, vegetable oil, animal oil, fatty acid methyl ester, epoxy fatty acid methyl esters, fatty acid glycerides, fatty acid isopropyl one or several. 具体凝胶测试方法为:在试管中将凝胶剂与溶剂以一定的质量比混合并加热至完全溶解,把所得溶液冷却,将试管倒置、管口向下,观察不到有溶液渗出或流下,并且晃动时没有破坏的产物,即认为形成凝胶。 DETAILED Gel Test method: a certain mass ratio and heated until completely dissolved in a mixed solvent with gel tube, the resulting solution was cooled, the tubes were inverted, nozzle down, there was not observed or oozing stream, and there is no damage to the product during shaking, i.e., that form a gel. 在本发明中,透过试管可以清晰看清楚试管背后物体形状时,则称该凝胶为透明凝胶;若不能,则称该凝胶为不透明凝胶。 In the present invention, we can clearly see through the tube behind the tube shape of the object, called the gel is a transparent gel; if not, the gel is called opaque gel.

[0080] 本发明所述的星形酯封端聚酰胺多元醇酯因其较好的凝胶性能可用于透明蜡烛的制造,具体方法为:星形酯封端聚酰胺多元醇酯作为凝胶剂与低极性溶剂在低于溶剂沸点高于溶剂凝固点温度之间混合成均相,加入或不加香精、颜料,倒入容器或模具中,加入烛芯,使烛芯部分被凝胶包裹,在室温或更低温度下冷却,制成透明蜡烛,聚酰胺多元醇酯占蜡烛总重的10%~90%,低极性溶剂为液体石蜡、轻质矿物油、棕榈油、大豆油、蓖麻油、葵花子油、油酸甲酯、大豆油酸甲酯、蓖麻油脂肪酸甲酯、环氧大豆油脂肪酸甲酯、油酸甲酯或是它们的混合物,优选矿物油、油酸甲酯、蓖麻油脂肪酸甲酯、环氧大豆油脂肪酸甲酯、辛癸酸甘油酯GTCC、肉豆蔻酸异丙酯IPM中的一种或几种;或是它们的混合物。 [0080] The star-ester-terminated polyamide of the present invention, the polyol ester due to its good performance can be used for the transparent gel candle manufacturing method specifically: a star polyol ester-terminated polyamide as a gelling ester agent with a low boiling point polar solvent is below the freezing point above the temperature of the mixture between the solvent to produce homogeneous, with or without flavor, a pigment, a mold or into the container, a wick was added to make a gel candle core portion is wrapped , cooled at room temperature or lower, made of a transparent candle, a polyamide polyol ester 10% to 90% of the total weight of the candle, the low polar solvent is liquid paraffin, light mineral oil, palm oil, soybean oil, castor oil, sunflower oil, methyl oleate, methyl soyate, castor oil fatty acid methyl ester, epoxidized methyl soyate, methyl oleate, or mixtures thereof, preferably a mineral oil, methyl oleate, castor oil fatty acid methyl ester, epoxidized methyl soyate, octyl caprate GTCC, isopropyl myristate IPM in one or more; or a mixture thereof. 本发明所述的星形酯封端聚酰胺多元醇酯由于可与多种低级性溶剂在较宽浓度范围形成凝胶,在人护理品、家居用品、户外固体燃料等诸多领域同样有较大的应用潜力。 Star-ester-terminated polyamide of the present invention, since a polyol ester with a variety of lower solvent to form a gel in a wide range of concentrations, in many areas of personal care products, household goods, outdoor solid fuels also have a greater the potential applications.

[0081] 本发明的有益效果:本发明通过分子设计,用更廉价、简便的方法对现有凝胶剂分子结构进一步改进,进一步增加凝胶分子中酯基、封端剂烃基的数量,在保持凝胶剂凝胶能力的同时,进一步降低分子极性,为解决上述问题提供理论和实践的支持,对进一步降低凝胶制品制造成本有重要的现实意义。 [0081] Advantageous Effects of Invention: The present invention by molecular design, a more inexpensive and simple method for the gel prior to further improve the molecular structure, further increasing the number of gels in the molecule an ester group, a hydrocarbon group capping agent, in while maintaining the ability to gel gel, to further reduce the molecular polarity, to provide support for the theory and practice to solve the above problems, there are important practical significance to further reduce manufacturing costs gel products.

[0082] 本发明所述的星形酯封端聚酰胺多元醇酯由于可与多种低级性溶剂在较宽浓度范围形成凝胶,在人护理品、家居用品、户外固体燃料等诸多领域同样有较大的应用潜力。 [0082] The star-ester-terminated polyamide of the present invention, since a polyol ester with a variety of lower solvent to form a gel in a wide range of concentrations, in many areas of personal care products, household goods, and other similar solid fuels outdoor there is great potential.

附图说明 BRIEF DESCRIPTION

[0083] 图1 一端为羧基的单十八醇酯封端聚二聚酸酰乙二胺(n=2)红外光谱。 [0083] FIG. 1 is a mono octadecyl end capped poly carboxy acid acid dimer diamine (n = 2) IR.

[0084] 图2单硬脂酸双十八醇酯封端聚二聚酸酰乙二胺甘油酯(n=2, 2、y=l、z=0) [0084] FIG. 2 monostearate, bis stearyl ester-terminated dimer acid poly glyceryl ethylenediaminetetraacetic acid (n = 2, 2, y = l, z = 0)

[0085] 图3 -端为羧基的单十八醇酯封端聚二聚酸酰乙二胺(n=l) [0085] Figure 3 - an end capped poly ethylenediamine acid dimer acid monostearyl esters carboxyl (n = l)

[0086] 图4十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=l,1,1,1、y=0、z=0) [0086] FIG. 4 capped poly octadecyl acid dimer acid diamine pentaerythritol (n = l, 1,1,1, y = 0, z = 0)

[0087] 图5十八醇酯封端聚二聚酸酰己二胺季戊四醇酯(n=l,1,1,l、y=0、z=0) [0087] FIG. 5 octadecyl terminated dimer acid polyethylene adipamide pentaerythritol (n = l, 1,1, l, y = 0, z = 0)

[0088] 图6十八醇酯封端聚二聚酸酰、己二酰乙二胺季戊四醇酯(n=l,1,1,1、y=0、z=0、 二聚酸:己二酸=9 :1) [0088] FIG. 6 capped poly octadecyl acid dimer acid, adipamide pentaerythritol (n = l, 1,1,1, y = 0, z = 0, dimer acids: adipic acid = 9: 1)

[0089] 图7十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=2, 2, 2, 2、y=0、z=0) [0089] FIG. 7 capped poly octadecyl acid dimer acid diamine pentaerythritol (n = 2, 2, 2, 2, y = 0, z = 0)

[0090] 图8十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=l,1,1,0、y=0、z=0) [0090] FIG. 8 capped poly octadecyl acid dimer acid diamine pentaerythritol (n = l, 1,1,0, y = 0, z = 0)

具体实施方式 detailed description

[0091] 以下的实施例用来说明本发明,但决不是对本发明范围的限制。 Example [0091] The following is to illustrate the invention, but in no way limit the scope of the present invention.

[0092] 实施例1单硬脂酸双十八醇酯封端聚二聚酸酰乙二胺甘油酯(n=2, 2、y=l、z=0) 的合成 [0092] Example 1 monostearate, bis stearyl ester-terminated dimer acid poly glyceryl ethylenediaminetetraacetic acid (n = 2, 2, y = l, z = 0) Synthesis of

[0093]步骤(1):按方程I,在氮气保护下,将100g(0. 178mol)二聚酸作为二元酸、 16.lg(0. 0593mol)十八醇作为一元醇加入250mL四口烧瓶,升温至70~80°C,加入7. 14g(0. 119mol)无水乙二胺作为二元胺,缓慢升温至210°C,反应4h,得具有式(4)分子结构的一端为羧基的单十八醇酯封端聚二聚酸酰乙二胺(n=2),酸值为29. 01 (理论值28. 18),化合物红外谱图(附图1)显示:3290.82cm1为酰胺NH伸缩振动,2920. 28cm\ 2851.27cm1为甲基、亚甲基伸缩振动吸收峰,1737. 72cm1为酯C=0伸缩振动吸收峰, 1711. 37cm1为羧酸C=0伸缩振动吸收峰,1637. 06cm1为酰胺C=0伸缩振动吸收峰,与目标化合物结构特征相符。 [0093] Step (1): According to equation I, under nitrogen atmosphere, 100g (. 0 178mol) dimer acid as a dibasic acid, 16.lg (. 0 0593mol) was added stearyl alcohol as a monoalcohol 250mL four the flask was warmed to 70 ~ 80 ° C, was added 7. 14g (0. 119mol) in anhydrous diamines as ethylenediamine was slowly warmed to 210 ° C, the reaction 4h, one end (4) have a molecular structure having the formula monostearyl alcohol esters of carboxy-terminated poly acid dimer acid diamine (n = 2), an acid value of 29.01 (28.18 of theory), IR spectrum of the compound (FIG. 1) display: 3290.82cm1 an amide NH stretching vibration, 2920. 28cm \ 2851.27cm1 methyl, methylene stretching vibration absorption peaks, 1737. 72cm1 ester C = 0 stretching vibration absorption peaks, 1711. 37cm1 carboxylic acid C = 0 stretching vibration absorption , 1637. 06cm1 an amide C = 0 stretching vibration absorption peaks, consistent with the structural characteristics of the target compound.

[0094] 步骤(2):按反应方程III,在氮气保护下,将10. 65g(0. 030mol)单硬脂酸甘油酯作为不饱和多元醇和酯加入步骤(1)制得的产物中,210°C反应lh,降温至160~180°C,加入〇.5g钛酸四丁酯缓慢升温至210°C反应24h,得具有式(8)、(17)结构的单硬脂酸双十八醇酯封端聚二聚酸酰乙二胺甘油酯(n=2,2、y=l、z=0),H00CR2C00H为二聚酸,二元酸:一元醇:二元胺:多元醇不饱和酯=6 : 2 : 4 : 1 (摩尔比),产品酸值1.77,用示差扫描量热法(DSC)测得化合物玻璃化转变温度Tg=98. 99°C,化合物红外谱图(附图2)显示: 3291. 32cm1为酰胺NH伸缩振动,2915. 87cm\2848. 30cm1为甲基、亚甲基伸缩振动吸收峰,1732. 25cm1为酯C=0伸缩振动吸收峰,且强度明显比一端为羧基的单十八醇酯封端聚二聚酸酰乙二胺(n=2)化合物酯C=0伸缩振动吸收峰增强,1711. 37cm1处羧酸C=0伸缩振动吸收峰已经消失表明酯化 [0094] Step (2): The reaction according to equation III, under nitrogen atmosphere, 10. 65g (. 0 030mol) glycerol monostearate ester as unsaturated polyol, added in step (1) in the product obtained, LH 210 ° C the reaction, was cooled to 160 ~ 180 ° C, 〇.5g tetrabutyl titanate was added slowly warm the reaction to 210 ° C 24h, to have the formula (8) monostearate, bis ten (17) of the structure eight capped poly esters dimer acid ethylene acid esters (n = 2,2, y = l, z = 0), H00CR2C00H dimeric acid, dibasic acid: the monohydric alcohol: diamine: polyol unsaturated ester = 6: 2: 4: 1 (molar ratio), Acid Number 1.77, compound glass by differential scanning calorimetry (DSC) as measured transition temperature Tg = 98 99 ° C, the infrared spectrum of the compound (. Figure 2) shows: 3291. 32cm1 stretching vibration of an amide NH, 2915 87cm \ 2848 30cm1 of methyl, methylene stretching vibration absorption peaks, 1732 25cm1 ester C = 0 stretching vibration absorption peak, and the intensity obvious. ratio of end carboxyl monostearyl alcohol esters capped poly acid dimer acid diamine (n = 2) an ester C = 0 stretching vibration absorption enhancement, at 1711. 37cm1 acid C = 0 stretching vibration absorption peak has disappearance show esterification 本完全,1637. 98cm1为酰胺C=0伸缩振动吸收峰且强度比一端为羧基的单十八醇酯封端聚二聚酸酰乙二胺(n=2)化合物酰胺C=0伸缩振动吸收峰降低,表明反应完全时化合物中酰胺键比例下降,与目标化合物结构特征相符。 This completely, 1637. 98cm1 an amide C = 0 stretching vibration and the peak intensity ratio of end carboxyl monostearyl alcohol esters capped poly acid dimer acid diamine (n = 2) Compound amide C = 0 stretching vibration peak reduction, indicated complete reaction of the compounds decrease the proportion of an amide bond, consistent with the structural characteristics of the target compound.

[0095] [0095]

Figure CN104058989BD00121

[0096] 式(17) [0096] Formula (17)

[0097] 单硬脂酸双十八醇酯封端聚二聚酸酰乙二胺甘油酯(n=2,2、y=l、z=0) [0097] monostearate, bis stearyl ester-terminated dimer acid poly glyceryl ethylenediaminetetraacetic acid (n = 2,2, y = l, z = 0)

[0098] 实施例2十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=l,1,1,l、y=0、z=0)的合成 Synthesis [0098] Example 2 capped poly octadecyl acid dimer acid diamine pentaerythritol (n = l, 1,1, l, y = 0, z = 0) of

[0099]步骤(1):按方程I,在氮气保护下,将100g(0. 178mol)二聚酸作为二元酸、 23. 66g(0. 089mol)十八醇作为一元醇加入250mL四口烧瓶,升温至70~80°C,加入5. 3g(0.089mol)无水乙二胺作为二元胺,缓慢升温至210°C,反应4h,得具有式(4)结构的一端为羧基的单十八醇酯封端聚二聚酸酰乙二胺(n=l),酸值为41. 17 (理论值40. 20),化合物红外谱图(附图3)显示3291. 81cm1为酰胺NH伸缩振动,2920. 43cm\2851. 58cm1 为甲基、亚甲基伸缩振动吸收峰,1737.67cm1为酯C=0伸缩振动吸收峰,1711. 34cm1为羧酸C=0伸缩振动吸收峰,1637. 50cm1为酰胺C=0伸缩振动吸收峰,与目标化合物结构特征相符。 [0099] Step (1): According to equation I, under nitrogen atmosphere, 100g (. 0 178mol) dimer acid as a dibasic acid, 23. 66g (. 0 089mol) was added stearyl alcohol as a monoalcohol 250mL four the flask was warmed to 70 ~ 80 ° C, was added 5. 3g (0.089mol) in anhydrous diamines as ethylenediamine was slowly warmed to 210 ° C, the reaction 4h, one end (4) to have a configuration of a carboxyl group of the formula monostearyl alcohol esters capped poly acid dimer acid diamine (n = l), an acid value of 41.17 (40.20 of theory), IR spectrum of the compound (FIG. 3) is displayed 3291. 81cm1 amide NH stretching vibration, 2920. 43cm \ 2851. 58cm1 of methyl, methylene stretching vibration absorption peaks, 1737.67cm1 ester C = 0 stretching vibration absorption peaks, 1711. 34cm1 carboxylic acid C = 0 stretching vibration absorption peaks, 1637 . 50cm1 an amide C = 0 stretching vibration absorption peaks, consistent with the structural characteristics of the target compound.

[0100] 步骤(2):按反应方程III,在氮气保护下,将3. 07g(0. 0223mol)季戊四醇作为多元醇加入步骤(1)制得的产物中,210°C反应lh,降温至160~180°C,加入0. 5g钛酸四丁酯作为催化剂缓慢升温至210°C反应24h,得具有式(14)、(18)结构的十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=l, 1,1,1、y=0、z=0),H00CR2C00H为二聚酸,二元酸:一元醇: 二元胺:多元醇=8 : 4 : 4 : 1 (摩尔比),产品酸值2. 15,用示差扫描量热法(DSC)测得化合物玻璃化转变温度Tg=96. 47°C,化合物红外谱图(附图4)显示:3290. 21cm1为酰胺NH伸缩振动,2920. 52cm\2851. 48cm1为甲基、亚甲基伸缩振动吸收峰,1739. 22cm1 为酯C=0伸缩振动吸收峰,1711. 34cm1处羧酸C=0伸缩振动吸收峰已经消失表明酯化基本完全,1638. 12cm1为酰胺C=0伸缩振动吸收峰,与目标化合物结构特征相符。 [0100] Step (2): The reaction according to equation III, under nitrogen atmosphere, 3. 07g (. 0 0223mol) pentaerythritol as polyhydric alcohol added in step (1) the product obtained, 210 ° C reaction LH, cooled to 160 ~ 180 ° C, was added 0. 5g of tetrabutyl titanate was slowly warmed to 210 ° C for 24h as a catalyst, to give formula (14), octadecyl (18) structure capped poly acetic acid dimer acid pentaerythritol diamine (n = l, 1,1,1, y = 0, z = 0), H00CR2C00H dimeric acid, dibasic acid: the monohydric alcohol: diamine: polyol = 8: 4: 4: 1 (molar ratio), Acid Number 2.15, compound glass by differential scanning calorimetry (DSC) as measured transition temperature Tg = 96 47 ° C, the infrared spectrum of the compound (Figure 4) shows: 3290. 21cm1 of amide NH stretching vibration, 2920. 52cm \ 2851. 48cm1 of methyl, methylene stretching vibration absorption peaks, 1739. 22cm1 ester C = 0 stretching vibration absorption peak at 1711. 34cm1 acid C = 0 stretching vibration showed absorption peak has disappeared substantially completely esterified, 1638. 12cm1 an amide C = 0 stretching vibration absorption peaks, consistent with the structural characteristics of the target compound.

[0101] [0101]

Figure CN104058989BD00131

[0102] 式(18) [0102] Formula (18)

[0103] 十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=l,1,1,l、y=0、z=0) [0103] stearyl acrylate capped poly dimer acid ethylenediamide pentaerythritol (n = l, 1,1, l, y = 0, z = 0)

[0104] 实施例3十八醇酯封端聚二聚酸酰己二胺季戊四醇酯(n=l,1,1,l、y=0、z=0)的合成 [0104] Example 3 octadecyl-terminated dimer acid polyethylene adipamide pentaerythritol (n = l, 1,1, l, y = 0, z = 0) Synthesis of

[0105] 按照实施例2的合成方法,依次加入100g(0. 178mol)二聚酸作为二元酸、23. 66g(0. 089mol)十八醇作为一元醇、10. 27g(0. 089mol)己二胺作为二元胺、 3. 07g(0. 0223mol)季戊四醇作为多元醇、0. 6g钛酸四丁酯作为催化剂反应制得具有式(14)、(19)结构的十八醇酯封端聚二聚酸酰己二胺季戊四醇酯(n=l,1,1,1、y=0、z=0), H00CR2C00H为二聚酸,二元酸:一元醇:二元胺:多元醇=8 : 4 : 4 : 1 (摩尔比),产品酸值1. 92,用示差扫描量热法(DSC)测得化合物玻璃化转变温度Tg=77. 02°C,化合物红外谱图(附图5)显示:3300. 43cm1为酰胺NH伸缩振动,2920. 30cm\2851.27cm1为甲基、亚甲基伸缩振动吸收峰,1738. 25cm1为酯C=0伸缩振动吸收峰,1710cm1左右处未发现羧酸c=0伸缩振动吸收峰表明酯化基本完全,1633. 34cm1为酰胺C=0伸缩振动吸收峰, 与目标化合物结构特征相符。 [0105] Synthesis according to the method of Example 2, were added 100g (0. 178mol) dimer acid as a dibasic acid, 23. 66g (0. 089mol) stearyl alcohol as a monoalcohol, 10. 27g (0. 089mol) hexanediamine as the diamine, 3. 07g (0. 0223mol) pentaerythritol as polyhydric alcohol, 0. 6g of tetrabutyl titanate as the catalyst prepared by the reaction of formula (14), octadecyl seal (19) of the structure dimer acid terminated poly adipamide pentaerythritol (n = l, 1,1,1, y = 0, z = 0), H00CR2C00H dimeric acid, dibasic acid: the monohydric alcohol: diamine: polyol = 8: 4: 4: 1 (molar ratio), Acid Number 1.92, a glass transition temperature of the compound Tg = 77 02 ° C as measured by differential scanning calorimetry (a DSC), IR spectrum of the compound (a. Figure 5) shows:. 3300 43cm1 stretching vibration of an amide NH, 2920 30cm \ 2851.27cm1 methyl, methylene stretching vibration absorption peaks, 1738 25cm1 ester C = 0 stretching vibration absorption peak was found at about 1710cm1. carboxylic acids c = 0 stretching vibration peak indicated essentially complete esterification, 1633. 34cm1 an amide C = 0 stretching vibration absorption peaks, consistent with the structural characteristics of the target compound.

[0106] [0106]

Figure CN104058989BD00141

[0107] 式(19) [0107] Formula (19)

[0108] 十八醇酯封端聚二聚酸酰己二胺季戊四醇酯(n=l,1,1,l、y=0、z=0) [0108] stearyl acrylate-terminated dimer acid polyethylene adipamide pentaerythritol (n = l, 1,1, l, y = 0, z = 0)

[0109] 实施例4十八醇酯封端聚二聚酸酰、己二酰乙二胺季戊四醇酯(n=l,1,1,1、y=0、 z=0、二聚酸:己二酸=9 : 1)的合成 [0109] Example 4 embodiment octadecyl capped poly acid dimer acid, adipamide pentaerythritol (n = l, 1,1,1, y = 0, z = 0, dimer acids: hexanoic acid = 9: 1) synthesis of

[0110] 按照实施例2的合成方法,将100g(0. 178mol)二聚酸、2.9g(0.0198mol)己二酸作为二元酸、26. 80g(0. 099mol)十八醇作为一元醇、6g(0. 099mol)乙二胺作为二元胺、 3. 3g(0. 0247mol)季戊四醇作为多元醇、0. 6g钛酸四丁酯作为催化剂依次加入四颈烧瓶进行反应制得具有式(14)、(18)结构的十八醇酯封端聚二聚酸酰、己二酰乙二胺季戊四醇酯(n=l,1,1,1、y=0、z=0、二聚酸:己二酸=9 :1),H00CR2C00H为二聚酸与己二酸的混合二元酸,二聚酸与己二酸投料摩尔比为9 : 1,二元酸:一元醇:二元胺:多元醇=8 : 4 : 4 : 1 (摩尔比)产品酸值2. 33,用示差扫描量热法(DSC)测得化合物玻璃化转变温度Tg=100. 89°C,化合物红外谱图(附图6)显示:3290. 79cm1为酰胺NH伸缩振动,2919. 02 cm\2850. 35cm1为甲基、亚甲基伸缩振动吸收峰,1737. 88cm1为酯C=0伸缩振动吸收峰, 1710cm1附近左右处未发现羧酸C=0伸 [0110] Synthesis according to the method of Example 2, the 100g (0. 178mol) dimer acid, 2.9g (0.0198mol) of adipic acid as a dibasic acid, 26. 80g (0. 099mol) monohydric alcohols as stearyl alcohol , 6g (0. 099mol) as diamine ethylenediamine, 3. 3g (0. 0247mol) pentaerythritol as polyhydric alcohol, 0. 6g of tetrabutyl titanate as a catalyst were added four-necked flask having the formula prepared by reacting ( 14), stearyl acrylate (18) structure capped poly acid dimer acid, adipamide pentaerythritol (n = l, 1,1,1, y = 0, z = 0, dimer acid : adipic acid = 9: 1), H00CR2C00H mixed dibasic acid dimer acid and adipic acid, dimer acid and adipic acid feed molar ratio of 9: 1, dibasic acid: the monohydric alcohol: diamines : polyol = 8: 4: 4: 1 (molar ratio) Acid Number 2.33, a glass transition temperature of the compound Tg = 100 89 ° C as measured by differential scanning calorimetry (a DSC), infrared spectra of compound (Figure 6) show:. 3290 79cm1 stretching vibration of an amide NH, 2919 02 cm \ 2850 35cm1 of methyl, methylene stretching vibration absorption peaks, 1737 88cm1 ester C = 0 stretching vibration absorption peaks, 1710cm1... No near around the C = 0 stretching acid 振动吸收峰表明酯化基本完全,1637. 98cm1为酰胺C=0伸缩振动吸收峰,与目标化合物结构特征相符。 Vibration absorption peaks showed essentially complete esterification, 1637. 98cm1 an amide C = 0 stretching vibration absorption peaks, consistent with the structural characteristics of the target compound.

[0111] 实施例5十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=2, 2, 2, 2、y=0、z=0)的合成 Octadecyl Synthesis Example 5 [0111] embodiment of the capped poly dimer acid ethylenediamide pentaerythritol (n = 2, 2, 2, 2, y = 0, z = 0) of

[0112] 按照实施例1的合成方法,将100g(0. 178mol)二聚酸作为二元酸、 16.lg(0. 0593mol)十八醇作为一元醇、7. 14g(0. 119mol)无水乙二胺作为二元胺、 2. 02g(0. 0148mol)季戊四醇作为多元醇、0. 45g钛酸四丁酯作为催化剂依次加入四颈烧瓶进行反应制得具有式(14)、(20)结构的十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=2, 2, 2, 2、y=0、z=0),H00CR2C00H为二聚酸,二元酸:一元醇:二元胺:多元醇=12 : 4 : 8 : 1(摩尔比),产品酸值1.71,用示差扫描量热法(DSC)测得化合物玻璃化转变温度Tg=98. 74°C,化合物红外谱图(附图7)显示:3289. 60cm1为酰胺NH伸缩振动,2920. 29 cm\2851. 27cm1为甲基、亚甲基伸缩振动吸收峰,1739. 05cm1为酯C=0伸缩振动吸收峰, 1710cm1附近左右处未发现羧酸C=0伸缩振动吸收峰表明酯化基本完全,1637. 48cm1为酰胺C=0伸缩振动吸收峰,与目标化合物结构特征相符。 [0112] Synthesis according to the method of Example 1, the 100g (0. 178mol) dimer acid as a dibasic acid, 16.lg (0. 0593mol) monohydric alcohols as stearyl alcohol, 7. 14g (0. 119mol) None water is a diamine ethylenediamine, 2. 02g (0. 0148mol) pentaerythritol as polyhydric alcohol, 0. 45g of tetrabutyl titanate as a catalyst were added four-necked flask prepared by reacting formula (14), (20) octadecyl structure capped poly dimer acid ethylenediamide pentaerythritol (n = 2, 2, 2, 2, y = 0, z = 0), H00CR2C00H dimeric acid, dibasic acid: the monohydric alcohol : diamine: polyol = 12: 4: 8: 1 (molar ratio), Acid Number 1.71, a glass transition temperature of the compound Tg = 98 74 ° C as measured by differential scanning calorimetry (a DSC), compound IR spectrum (Figure 7) show:. 3289 60cm1 stretching vibration of an amide NH, 2920 29 cm \ 2851 27cm1 of methyl, methylene stretching vibration absorption peaks, 1739 05cm1 ester C = 0 stretching vibration absorption... peak near about at 1710cm1 No acid C = 0 stretching vibration absorption peak indicated essentially complete esterification, 1637. 48cm1 an amide C = 0 stretching vibration absorption peaks, consistent with the structural characteristics of the target compound.

[0113] [0113]

Figure CN104058989BD00151

[0114] 式(20) [0114] Formula (20)

[0115] 十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=2, 2, 2, 2、y=0、z=0) [0115] stearyl acrylate capped poly dimer acid ethylenediamide pentaerythritol (n = 2, 2, 2, 2, y = 0, z = 0)

[0116] 实施例6十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=l,1,l,0、y=0、z=0)的合成 Synthesis [0116] Example 6 octadecyl capped poly dimer acid ethylenediamide pentaerythritol (n = l, 1, l, 0, y = 0, z = 0) of

[0117] 按照实施例2的合成方法,控制反应物比例,将100g(0. 178mol)二聚酸作为二元酸、27.6g(0.102mol)十八醇作为一元醇、4.6g(0.0763mol)乙二胺作为二元胺、 3.47g(0.0254m〇l)季戊四醇、0. 5g钛酸四丁酯反应制得具有式(14)结构的十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(ri=l,1,1,0、y=〇、z=0),其中n=l单十八醇酯封端聚酰胺支链与n=0单十八醇酯封端聚酰胺支链(二聚酸单十八醇酯支链)数量比为3 : 1,H00CR2C00H 为二聚酸,二元酸:一元醇:二元胺:多元醇=7 : 4 : 3 : 1 (摩尔比),产品酸值2. 10, 用示差扫描量热法(DSC)测得化合物玻璃化转变温度Tg=88.40°C,化合物红外谱图(附图8)显示:3290. 40cm1为酰胺NH伸缩振动,2920. 03cm\2851. 15cm1为甲基、亚甲基伸缩振动吸收峰1738.67cm1为酯C=0伸缩振动吸收峰1710cm1附近左右处未发现羧酸C=0 伸缩振动吸收峰表明酯化基本完全,1637. 76cm [0117] Synthesis according to the method of Example 2, controlling the ratio of reactants, the 100g (0. 178mol) dimer acid as a dibasic acid, 27.6g (0.102mol) as a monohydric alcohol stearyl alcohol, 4.6g (0.0763mol) as the diamines ethylenediamine, 3.47g (0.0254m〇l) pentaerythritol, 0. 5g of tetrabutyl titanate was prepared by the reaction of formula (14) octadecyl structure capped poly dimer acid ethylenediamide pentaerythritol (ri = l, 1,1,0, y = square, z = 0), where n = l monostearyl ester-terminated polyamide alcohols and branched chain mono n = 0 octadecyl-terminated polyamide (dimer acid mono branched octadecyl) number of branches ratio 3: 1, H00CR2C00H dimeric acid, dibasic acid: the monohydric alcohol: diamine: polyol = 7: 4: 3: 1 (molar ratio), the product acid number of 2.10, by differential scanning calorimetry (DSC) as measured glass transition temperature of the compound Tg = 88.40 ° C, the infrared spectrum of the compound (Figure 8) show:. 3290 40cm1 an amide NH stretching vibration, 2920. 03cm \ 2851. 15cm1 of methyl, methylene 1738.67cm1 stretching vibration absorption peak of the ester C = 0 stretching vibration peak near about at 1710cm1 No acid C = 0 stretching vibration absorption peaks showed substantially esterified completely, 1637. 76cm 1为酰胺C=0伸缩振动吸收峰,与目标化合物结构特征相符。 1 is an amide C = 0 stretching vibration absorption peaks, consistent with the structural characteristics of the target compound.

[0118] 实施例7星形酯封端聚酰胺多元醇酯作凝胶剂的有机凝胶制备 Preparation of polyamides as gelling agent a polyol ester of an organic gel [0118] Example 7 Example star esterterminated

[0119] 在试管中将凝胶剂分别与低极性溶剂液体石蜡、油酸甲酯、环氧大豆油酸甲酯、大豆油以一定的质量比混合并加热至完全溶解,把所得溶液冷却,将试管倒置、管口向下,观察不到有溶液渗出或流下,并且晃动时没有破坏的产物,即认为形成凝胶,在本发明中,透过试管可以清晰看清楚试管背后物体形状时,则称该凝胶为透明凝胶,若不能,则称该凝胶为不透明凝胶。 [0119] In a test tube gels are liquid paraffin and a low polar solvent, methyl oleate, epoxidized soybean oil methyl ester, soybean oil and a certain mass ratio of heated until complete dissolution, the resulting solution was cooled the tubes were inverted, nozzle down, there was not observed or bleed stream, and there is no product damage during shaking, i.e., that form a gel in the present invention, can clearly see through the tube behind the tube shape of the object when, called the gel is a transparent gel, if not, the gel is called opaque gel.

[0120] 以实施例1中合成的单硬脂酸双十八醇酯封端聚二聚酸酰乙二胺甘油酯(n=2, 2、y=l、z=0)制得的凝胶、以实施例2中合成的十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=l,1,1,1、y=0、z=0)制得的凝胶、以实施例3中合成的十八醇酯封端聚二聚酸酰己二胺季戊四醇酯(n=l, 1,1,1、y=0、z=0)制得的凝胶、以实施例4中合成的十八醇酯封端聚二聚酸酰、己二酰乙二胺季戊四醇酯(ri=l,1,1,1、7=0、2=0、二聚酸:己二酸=9:1)制得的凝胶、以实施例5中合成的十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=2, 2, 2, 2、y=0、 z=0)制得的凝胶剂对上述四种溶剂凝胶效果相同,具体凝胶效果如下表所示: [0120] In embodiments monostearate, bis stearyl ester synthesized in Example 1 capped poly ethylenediaminetetraacetic acid dimer acid ester (n = 2, 2, y = l, z = 0) of the condensate obtained stearyl ester gum, synthesized in Example 2 capped poly dimer acid ethylenediamide pentaerythritol (n = l, 1,1,1, y = 0, z = 0) the gel obtained, in embodiments octadecyl Example 3 synthesis of poly-terminated dimer acid adipamide pentaerythritol (n = l, 1,1,1, y = 0, z = 0) the gel obtained to implement octadecyl synthesized in Example 4 terminated poly acid dimer acid, pentaerythritol adipamide (ri = l, 1,1,1,7 = 0,2 = 0, dimer acids: adipic acid = 9: 1 octadecyl) gel was prepared, in Example 5 synthesis of acid terminated poly dimer acid diamine pentaerythritol (n = 2, 2, 2, 2, y = 0, z = 0) of the same gel prepared above four sol-gel effect, particularly the effect of the gel shown in the following table:

[0121] 表1 [0121] TABLE 1

[0122] [0122]

Figure CN104058989BD00161

[0123] 以实施例6中合成的十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=l,1,1,0、 y=〇、z=〇)制得的凝胶剂凝胶效果如下表所示: [0123] In octadecyl Example 6 Synthesis of acid terminated poly dimer acid diamine pentaerythritol (n = l, 1,1,0, y = square, z = square) gel prepared gels results in the following table:

[0124]表2 [0124] TABLE 2

[0125] [0125]

Figure CN104058989BD00162

[0126] 实施例8星形酯封端聚酰胺多元醇酯作凝胶剂的透明蜡烛的制备 Example 8 Preparation of Transparent candles star-terminated [0126] Embodiment polyamide polyol esters as gel

[0127] 以实施例6中合成的十八醇酯封端聚二聚酸酰乙二胺季戊四醇酯(n=l,1,1,0、 y=0、z=0)作为凝胶剂,取30g凝胶剂加入70g液体石錯中,加热溶液澄清透明,倒入模具中,加入烛芯,冷却至室温,得无色透明矿物油蜡烛,蜡烛火焰高度为2cm,燃烧时火焰稳定明亮。 [0127] In embodiments in Example 6 Synthesis of octadecyl capped poly dimer acid ethylenediamide pentaerythritol (n = l, 1,1,0, y = 0, z = 0) as a gelling agent, 30g of liquid gelling agent added 70g stone and error, clear and transparent solution was heated, poured into a mold, a wick was added, cooled to room temperature to give a transparent mineral oil candles, flame height is 2cm, bright and stable combustion flame.

Claims (7)

  1. 1. 一种星形酯封端聚酰胺多元醇酯化合物,该化合物结构如下通式(1)所示: A star polyol ester-terminated polyamide ester compounds, compounds of the following general formula (1):
    Figure CN104058989BC00021
    所述通式为Rt(OH)t的多元醇是:丙三醇、三羟甲基甲烧、三羟甲基乙烧、三羟甲基丙烷、季戊四醇; 其中, T表示通式为Rt(OH)t的多元醇所含羟基的数量,T=3或4 ; Rl是C4-C24的烃基; R2是C4-C42的烃基; R3是C2-C12的烃基; R4是C1-C23的烃基; n表示各支链中重复单元的数量,各支链间的n值可以相等也可不等,可以等于0但不全为0,且数值为0~3; X表示化合物中具有通式(2)分子结构支链的数量,2 <X< 4 ; The formula polyol Rt (OH) t is: glycerol, trimethylol for methane, trimethylol burned acetate, trimethylol propane, pentaerythritol; wherein, T represents the general formula Rt ( OH) t number of hydroxyl groups contained in the polyol, T = 3 or 4; Rl is a C4-C24 hydrocarbon; R2 is C4-C42 hydrocarbon group; R3 is C2-C12 hydrocarbon group; R4 is a C1-C23 hydrocarbon group; n represents the number of repeating units in each chain, branched, n is a value between the respective branches and the like may not be equal, but may be equal to 0 are not all zeros, and the value is 0 ~ 3; X represents a compound having the general formula (2) molecular number branched structure, 2 <X <4;
    Figure CN104058989BC00022
    式⑵ y表示化合物中具有通式(3)分子结构支链的数量,0 <y< 2 ;x+y=3或4 ; ⑵ y represents the number of compound of formula (3) of a branched molecular structure having the general formula, 0 <y <2; x + y = 3 or 4;
    Figure CN104058989BC00023
    式⑶ x+y=T0 Formula ⑶ x + y = T0
  2. 2. 根据权利要求1所述的星形酯封端聚酰胺多元醇酯化合物,其特征在于:所述通式SRt(OH)t的多元醇是:丙三醇、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷、季戊四醇;含有至少3条用酯键连接的支链,其中至少2条支链是具有通式(2)分子结构的支链,化合物分子呈多支链的星形结构。 The ester-terminated polyamide star polyol ester compound according to claim 1, wherein: said general formula SRt (OH) t polyols are: glycerol, trimethylol methane, tris trimethylol ethane, trimethylol propane, pentaerythritol; a branched ester linkage with at least 3, wherein at least two branched chain having the general formula (2) a branched molecular structure, the compound molecules form multi-branching chain star structure.
  3. 3. -种权利要求1~2任一项所述的星形酯封端聚酰胺多元醇酯化合物的制备方法, 其特征在于,所述方法包括如下步骤: 步骤(1)单封端聚酰胺的制备: 将二元酸、二元胺、一元醇以一定摩尔比混合反应制得具有通式(4)分子结构的一端为羧基的单封端聚酰胺, 式⑷ 3. - star-terminated any one of claims 1 to 2 kinds of polyamides as claimed in claim preparing a polyol ester compound, wherein the method comprises the following steps: (1) single-terminated polyamide preparation: the dibasic acid, diamine, certain monohydric alcohol prepared by reacting a molar ratio of the general formula (4) at one end of the molecular structure of a carboxyl group-terminated polyamide single formula ⑷
    Figure CN104058989BC00031
    Rl是C4-C24的烃基; R2是C4-C42的烃基; R3是C2-C12的烃基;n表示重复单元的数目,n< 3 ; 所得单封端聚酰胺根据反应投料比的不同,是一种具有通式(4)结构的单封端聚酰胺,或几种具有通式(4)结构但相互之间n值不同的单封端聚酰胺组成的混合物; 步骤(2)星形酯封端聚酰胺多元醇酯化合物的制备: 将多元醇或不饱和多元醇酯与步骤(1)制得的单封端聚酰胺、一元酸、催化剂按一定比例混合进行酯化反应制得通式(1)结构的星形酯封端聚酰胺多元醇酯化合物; 所述的二元酸为二聚酸,或二聚酸与己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸中的任意一种或几种的混合物,混合物中二聚酸摩尔含量大于50% ; 所述的二元胺为乙二胺、1,2-丙二胺、1,3-丙二胺、2, 2-二甲基-1,3-丙二胺、1,4- 丁二胺、1,5-戊 Rl is a hydrocarbon radical C4-C24 a; R2 is hydrocarbyl C4-C42's; R3 is a hydrocarbon group C2-C12 a; n-represents the number of repeating units, n <3; monocapped obtained polyamide different depending on the reaction feed ratio, is a species having a single-terminated polyamide of formula (4) structure, or more having the general formula (4) structure but mutually different values ​​of n single-terminated polyamide mixtures thereof; step (2) ester-star preparation of polyol ester terminated polyamide compound: polyol or unsaturated polyol ester of step (1) single-terminated prepared polyamide, a monobasic acid, by mixing a catalyst for esterification general formula ( 1) ester-terminated star-shaped configuration of the polyamide polyol ester compound; the dicarboxylic acid is dimer acid, dimer acid or with adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid of any one or more of a mixture of dimer acid mixture the molar content of greater than 50%; the diamines are ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,4-butanediamine, 1, pentyl 5- 二胺、2-甲基-1,5-戊二胺、1,6-己二胺、环己二胺、1,7-庚二胺、1,8-辛二胺、1,9-壬二胺、癸二胺、十二烷二元胺,或为上述二元胺以任意比例混合组成的混合物; 所述的一元醇是正己醇、正庚醇、正辛醇、异辛醇、壬醇、癸醇、十二醇、十四醇、十六醇、 十八醇、二十烷醇、二十二烷醇或是上述一元醇任意比例混合组成的混合物; 所述的多元醇是丙三醇、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷、季戊四醇;不饱和多元醇酯是上述多元醇的单酯或多酯; 所述的一元酸是正辛酸、正癸酸、十二酸、十四酸、十六酸、十八酸、二十烷酸、二十二烷酸、二十四烷酸、二十八烷酸或是上述一元酸以任意比例混合组成的混合物; 所述的催化剂是钛酸四丁酯、氯化亚锡、二月桂酸二丁基锡中的一种,催化剂的用量为反应物质量总和的0. 1%~1%。 Diamine, 2-methyl-1,5-diamine, hexamethylene diamine, cyclohexylene diamine, heptamethylene diamine, octamethylene diamine, 1,9-nonane diamine, decane diamine, dodecane diamine, or a mixture of the above diamine mixed in any proportion thereof; said monohydric alcohols are n-hexanol, n-heptanol, n-octanol, i-octanol, nonanol alcohol, decanol, dodecanol, tetradecyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, behenyl alcohol, or the monovalent alcohol consisting of a mixture in any ratio of mixture; said polyol is prop triol, trimethylol methane, trimethylol ethane, trimethylol propane, pentaerythritol; ester is an unsaturated polyol ester of mono- or polyhydric alcohols; the monobasic acid is n-octanoic acid, n-decyl acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosanoic acid, behenic acid, lignoceric acid, octacosanoic acid or a monobasic acid mixture composition at an arbitrary ratio mixtures thereof; said catalyst is tetrabutyl titanate, stannous chloride, dibutyl tin dilaurate in an amount of catalyst is 0.1% to 1% of the total mass of the reactants.
  4. 4. 根据权利要求3所述的星形酯封端聚酰胺多元醇酯化合物的制备方法,其特征在于: 步骤(1)单封端聚酰胺的制备中二元酸、二元胺、一元醇反应摩尔比为4~2: 3~1: 1,反应温度为150°C~250°C; 步骤(2)酯封端聚酰胺多元醇酯化合物的制备中单封端聚酰胺、一元酸、多元醇的摩尔比为12~2:10~0:1~0• 6,反应温度为150°C~250°C; 步骤(2)酯封端聚酰胺多元醇酯化合物的制备中单封端聚酰胺、不饱和多元醇酯的摩尔比为11~2:1~0• 6,反应温度为150°C~250°C。 The star-ester according to claim 3 Preparation polyol ester terminated polyamide compound, comprising the steps of: (1) preparation of a single dibasic acid-terminated polyamide, a diamine, a monohydric alcohol the reaction molar ratio of from 4 to 2: 3 to 1: 1, reaction temperature is 150 ° C ~ 250 ° C; step (2) ester-terminated polyamide prepared in a single-terminated polyamide polyol ester compound, a monobasic acid, the molar ratio of polyol is 12 ~ 2: 10 ~ 0: 1 ~ 0 • 6, the reaction temperature is 150 ° C ~ 250 ° C; step (2) ester-terminated polyamide polyol ester compound prepared in monocapped polyamide, the molar ratio of the unsaturated polyol ester is 11 ~ 2: 1 ~ 0 • 6, the reaction temperature is 150 ° C ~ 250 ° C.
  5. 5. 权利要求1~2任一项所述星形酯封端聚酰胺多元醇酯化合物的应用,其特征在于: 其作为凝胶剂与低极性溶剂在低于溶剂沸点高于溶剂凝固点温度之间混合成均相,在室温或更低温度下冷却,形成有机凝胶,星形酯封端聚酰胺多元醇酯占有机凝胶总重的5%~ 90% 〇 The star-1-2 according to claim 5. The ester-terminated polyamide applications polyol ester compound, wherein: as a gelling agent and a low polar solvent below the boiling point temperature higher than the freezing point of the solvent between the mixing into a homogeneous, cooled at room temperature or below, to form an organic gel, ester-terminated polyamide star polyol ester occupies 5% to 90% of the total weight of the organogel billion
  6. 6. 根据权利要求5所述的星形酯封端聚酰胺多元醇酯化合物的应用,其特征在于:所述低极性溶剂为:矿物油、植物油、动物油、脂肪酸甲酯、环氧脂肪酸甲酯、脂肪酸甘油酯、月旨肪酸异丙酯中的一种或几种。 The star-ester-terminated polyamide according to application 5 polyhydric alcohol ester compound as claimed in claim, wherein: said low-polarity solvent: mineral oil, vegetable oil, animal oil, fatty acid methyl ester, epoxy fatty acid methyl esters, fatty acid glycerides, fatty acid iso-month purpose one or more of propylene.
  7. 7. 根据权利要求6所述的星形酯封端聚酰胺多元醇酯化合物的应用,其特征在于:所述低极性溶剂为:液体石蜡、轻质矿物油、棕榈油、大豆油、蓖麻油、葵花子油、油酸甲酯、大豆油酸甲酯、蓖麻油脂肪酸甲酯、环氧大豆油脂肪酸甲酯、辛癸酸甘油酯GTCC、肉豆蔻酸异丙酯IPM中的一种或几种。 The star-ester according to claim 6 applied terminated polyamide polyol ester compound, wherein: said solvent is a low polarity: liquid paraffin, light mineral oil, palm oil, soybean oil, castor sesame oil, sunflower oil, methyl oleate, methyl soyate, castor oil fatty acid methyl ester, epoxidized methyl soyate, octyl caprate GTCC, isopropyl myristate IPM of one or several species.
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CN1238678A (en) * 1996-10-18 1999-12-15 友联坎普公司 Ester-terminated polyamide gels
CN1335762A (en) * 1999-01-04 2002-02-13 国际纸业公司 Tertiary amide terminated polyamides and uses thereof

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Publication number Priority date Publication date Assignee Title
CN1238678A (en) * 1996-10-18 1999-12-15 友联坎普公司 Ester-terminated polyamide gels
CN1335762A (en) * 1999-01-04 2002-02-13 国际纸业公司 Tertiary amide terminated polyamides and uses thereof

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