阅读说明：本技术 一种皮革脱脂剂及其制备方法和应用 (Leather degreasing agent and preparation method and application thereof ) 是由 刘子龙 应班 梁帅 赵余徉 胡鹛元 李祥 陈明亮 李磊 李方 于 2020-06-15 设计创作，主要内容包括：本发明公开一种皮革脱脂剂及其制备方法和应用。脱脂剂,其包含一种、两种、三种或更多种选自如下式(I)所示的异构醇嵌段聚醚：RO[CH<Sub>2</Sub>CH(CH<Sub>3</Sub>)O]<Sub>n</Sub>(CH<Sub>2</Sub>CH<Sub>2</Sub>O)<Sub>m</Sub>H(I)其中,R选自平均异构化度≥2的异构烷基；n选自1-8的数；m选自0.5-15的数。该脱脂剂具有良好的渗透及乳化作用,可有效的降低皮胚内的油脂含量；该加脂剂适用于牛皮,羊皮,猪皮等皮件的加工脱脂。(The invention discloses a leather degreasing agent, and a preparation method and application thereof. Degreasing agents comprising one, two, three or more heterogeneous alcohol-block polyethers selected from the group consisting of those represented by the following formula (I): RO [ CH ] 2 CH(CH 3 )O] n (CH 2 CH 2 O) m H (I), wherein R is selected from isomeric alkyl groups with an average isomerization degree of more than or equal to 2; n is selected from the group consisting of 1-8; m is selected from a number from 0.5 to 15. The degreasing agent has good permeation and emulsification effects, and can effectively reduce the oil content in the skin embryo; the fatting agent is suitable for degreasing leather products such as cow leather, sheep leather, pigskin and the like.)

1. A degreaser comprising one, two, three or more heterogeneous alcohol block polyethers selected from those of the following formula (I):

RO[CH₂CH(CH₃)O]_n(CH₂CH₂O)_mH (I)

wherein R is selected from isomeric alkyl with average isomerization degree more than or equal to 2;

n is selected from the group consisting of 1-8;

m is selected from a number from 0.5 to 15.

2. Degreasing agent according to claim 1, wherein the isomeric alkyl groups are selected from C_5-20At least one of the isomeric alkyl radicals, preferably C_8-14At least one of isomeric alkyl groups; the average degree of isomerization of the isomeric alkyl group means the average number of branches in the isomeric alkyl group;

preferably, the average degree of isomerization is selected from a number above 2, preferably a number of 2 to 10;

preferably, R is selected from C with an average degree of isomerization of 2 or 3₁₀、C₁₁、C₁₂、C₁₃An isomeric alkyl group;

preferably, R is selected from one of the following groups:

C₃H₇CH(CH₃)CH₂CH(CH₃)C₃H₆-、

C₃H₇CH(CH₃)CH₂CH₂CH(CH₃)C₃H₆-、

C₅H₁₁CH(CH₃)CH₂CH₂CH(CH₃)C₃H₆-、

C₃H₇CH(CH₃)CH₂CH(CH₃)CH₂CH(CH₃)C₂H₄-、

CH₃C₂H₄CH(CH₃)CH₂CH(CH₃)C₂H₄-；

preferably, each branch in the isomeric alkyl groupIdentical or different, independently of one another, from C_1-6Linear or branched alkyl of (a);

preferably, when there are more than 2 branches in R, the branches are respectively located on adjacent or non-adjacent carbon atoms on the main chain of R;

preferably, n is an integer or a decimal number, such as a number selected from 1 to 6;

preferably, m is an integer or a decimal number, such as a number selected from 0.5 to 10.

3. Degreasing agent according to claim 1 or 2, characterized in that the isomeric alcohol-block polyethers are selected from the structures represented by the following formulae (i), (ii), (iii) or (iv):

wherein m and n independently have the definitions as set forth in claim 1; preferably m is a number from 0.5 to 10 and n is a number from 1 to 6;

more preferably, the isomeric alcohol block polyether has a structure selected from the group consisting of the following formulas (1), (2), (3), (4), (5) and (6):

4. a degreaser according to any of claims 1 to 3, comprising at least two, preferably three structurally different isomeric alcohol block polyethers;

preferably, the degreaser comprises three isomeric alcohol block polyethers with different HLB values;

preferably, the three isomeric alcohol block polyethers differ in their HLB value and are selected independently of one another from 8 to 15;

preferably, the three isomeric alcohol block polyethers are each selected from compounds C having a compound A, HLB value between 8 and 11 and a compound B, HLB value between greater than 13 and equal to or less than 15, having an HLB value between greater than 11 and equal to or less than 13;

compounds A, B and C have a structure according to formula (I), preferably according to formula (I), (ii), (iii), (iv) and/or (v); more preferably having a structure as described in formulas (1) to (6);

preferably, the HLB value of compound a is 8.5 to 10.5;

preferably, the HLB value of compound B is 11.5 to 12.5;

preferably, the HLB value of compound C is 13.5 to 14.5;

preferably, the amount of compound a is greater than the amount of compound B and/or compound C;

preferably, the degreasing agent further comprises an organic solvent and/or water.

5. Degreasing agent according to any of claims 1-4, characterized in that the degreasing agent comprises the following components in parts by weight:

20-70 parts of isomeric alcohol block polyether;

1-15 parts of an organic solvent;

20-60 parts of water;

the isomeric alcohol block polyether comprises three isomeric alcohol block polyethers with different HLB values; preferably, compound C having compound B, HLB value between greater than 13 and equal to or less than 15 with compound A, HLB value between 8 and 11 HLB value between greater than 11 and equal to or less than 13;

preferably, the organic solvent is one or a mixture of more than two of ethylene glycol, propylene glycol, ethylene glycol monobutyl ether and isopropanol;

preferably, the degreaser further optionally comprises a biocide; preferably, when present, the weight parts of the bactericide are 0.01-0.2 parts;

preferably, the bactericide is morpholine and/or benzisothiazolinone.

6. A method of preparing a degreaser according to any of claims 1 to 5, comprising mixing the components thereof; preferably, the components are uniformly mixed according to the parts by weight of claim 5.

7. A method of degreasing a leather article, comprising contacting the leather article with the degreaser of any of claims 1-5.

8. A method of reducing the oil content of a leather item or article, the method comprising contacting the leather item with a degreaser according to any of claims 1 to 5.

9. Use of a degreasing agent according to any of claims 1-5 for degreasing a leather item, preferably for degreasing after immersion in water and/or degreasing after bating;

preferably, the leather piece is a hide, preferably an animal hide, such as cow hide, sheep hide or pig hide.

10. Leather comprising one, two, three or more isomeric alcohol block polyethers as defined in any one of claims 1 to 4; preferably, the leather comprises leather pieces processed by the isomeric alcohol block polyether;

preferably, the leather is prepared from the leather article of claim 9.

Technical Field

The invention belongs to the field of leather additives, and particularly relates to a leather degreasing agent, and a preparation method and application thereof.

Background

Leather generally refers to animal skins which are obtained by physical and chemical processing such as unhairing and tanning and are denatured and non-perishable. The leather is formed by tightly weaving natural protein fibers in a three-dimensional space, and the surface of the leather is provided with a special grain surface layer which has natural grains and luster and comfortable hand feeling. The process of processing hides into leather mainly comprises three stages of preparation, tanning and finishing. Wherein the preparation phase comprises the steps of soaking, fleshing, liming for dehairing, bating, pickling and the like, so that the hides are in a state ready to be tanned. The tanning stage is a quality change stage for converting the hide into leather, and the tanning changes the structural stability of collagen, so that the physical and chemical properties and the sanitation of the leather are improved. In the finishing stage, leather is finished mainly from the perspective of beauty and commodity requirements, such as dyeing, softening, flattening, finishing and the like. In the preparation phase, the oil and fat in the skin of the raw leather rich in oil and fat can prevent various leather chemicals from penetrating into the skin and combining with the collagen fibers of the skin. Meanwhile, if the removal rate of the grease in the leather is low in the leather making process, the grease which is not removed from the finished leather can be transferred to the surface of the leather to form grease. Therefore, degreasing plays a very important role in raw hides rich in oil and fat.

The main defatting methods at present are lipase defatting method and surfactant defatting method. Wherein, the lipase degreasing method is to catalyze the hydrolysis of intradermal grease by lipase to generate glycerol, fatty acid, monoglyceride and diglyceride so as to achieve the purpose of degreasing; the surfactant degreasing is realized by emulsifying the intradermal oil by an emulsifying method. The two methods are the most used degreasing methods at present, wherein the surfactant degreasing method is simple and convenient to operate and small in production risk coefficient, and leather goods cannot be damaged due to improper control. However, the degreasing effect of the surfactant on the intradermal oil and fat in the prior market is poor, and the anionic surfactant is used as a main component, so that the anionic surfactant is remained, and the combination of the subsequent material and the leather is influenced.

Disclosure of Invention

In order to improve the problems in the prior art, the invention provides a degreasing agent, which comprises one, two, three or more kinds of isomeric alcohol block polyethers selected from the following formula (I):

RO[CH₂CH(CH₃)O]_n(CH₂CH₂O)_mH (I)

wherein R is selected from isomeric alkyl with average isomerization degree more than or equal to 2;

n is selected from the group consisting of 1-8;

m is selected from a number from 0.5 to 15.

According to an embodiment of the invention, the isomeric alkyl radicals may be chosen from C_5-20At least one of the isomeric alkyl radicals, for example, may be C_8-14At least one of the isomeric alkyl groups. Illustratively, the isomeric alkyl groups may be selected from C₉Isomeric alkyl radicals, C₁₀Isomeric alkyl radicals, C₁₁Isomeric alkyl radicals, C₁₂Isomeric alkyl radicals, C₁₃At least one of the isomeric alkyl groups.

According to an embodiment of the invention, the average degree of isomerization of the isomeric alkyl group means the average number of branches in the isomeric alkyl group.

It will be appreciated by those skilled in the art that the average degree of isomerization may be an integer or a decimal number. For example, the average degree of isomerization may be selected from values above 2, such as values from 2 to 10. As an example, the average degree of isomerization may be selected from a number of 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 5.0, or higher.

According to exemplary embodiments of the invention, R may be selected from C having an average degree of isomerization of 2 or 3₁₀、C₁₁、C₁₂、C₁₃An isomeric alkyl group.

According to an exemplary embodiment of the invention, R may be selected from one of the following groups:

C₃H₇CH(CH₃)CH₂CH(CH₃)C₃H₆-、

C₃H₇CH(CH₃)CH₂CH₂CH(CH₃)C₃H₆-、

C₅H₁₁CH(CH₃)CH₂CH₂CH(CH₃)C₃H₆-、

C₃H₇CH(CH₃)CH₂CH(CH₃)CH₂CH(CH₃)C₂H₄-、

CH₃C₂H₄CH(CH₃)CH₂CH(CH₃)C₂H₄-。

according to an embodiment of the invention, each branch of said isomeric alkyl radicals, which may be identical or different, is chosen, independently of the others, from C_1-6Such as methyl, ethyl, n-propyl or isopropyl.

According to an embodiment of the present invention, when there are more than 2 branches in R, the branches may be respectively located on adjacent or non-adjacent carbon atoms on the main chain of R.

According to an embodiment of the invention, n may be an integer or a decimal number, such as a number selected from 1 to 6, for example a number from 1.5 to 4.5, exemplarily n may be selected from 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.3, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0.

According to an embodiment of the invention, m may be an integer or a decimal number, such as a number selected from 0.5 to 10, e.g. a number of 0.5, 0.8, 1.0, 2.0, 3.0, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5.

Illustratively, the isomeric alcohol block polyether may have a structure selected from the group consisting of the following formulas (i), (ii), (iii), or (iv):

wherein m and n independently have the definitions described above; preferably, m is a number from 0.5 to 10 and n is a number from 1 to 6.

More preferably, the isomeric alcohol block polyether may have a structure selected from the group consisting of the following formulas (1), (2), (3), (4), (5) or (6):

according to an embodiment of the invention, the degreasing agent comprises at least two, preferably three, structurally different isomeric alcohol block polyethers selected from compounds of the structure shown in formula (I).

According to a preferred embodiment of the invention, the degreaser comprises three isomeric alcohol block polyethers having different HLB values. Wherein the HLB value represents a hydrophilic-hydrophobic Balance value (Hydrophile-Lipophile Balance Number).

According to a preferred embodiment of the invention, the three isomeric alcohol block polyethers differ in their HLB value and are selected independently of one another from 8 to 15.

According to an embodiment of the invention, the three isomeric alcohol block polyethers are each chosen from compounds C having a compound A, HLB value between 8 and 11 and a compound B, HLB value between greater than 13 and equal to or less than 15, having an HLB value between greater than 11 and equal to or less than 13;

compounds A, B and C have a structure according to formula (I), preferably according to formula (I), (ii), (iii), (iv) and/or (v); more preferably, the compound has the structure described in the formulas (1) to (6).

According to an embodiment of the invention, said compound a has an HLB value of 8.5 to 10.5, for example 8, 8.5, 9, 9.5, 10, 10.5, 11.

According to an embodiment of the invention, the compound B has an HLB value of 11.5 to 12.5, e.g. 11.5, 12, 12.5, 13.

According to an embodiment of the invention, said compound C has an HLB value of 13.5 to 14.5, such as 13.5, 14, 14.5, 15.

According to an embodiment of the invention, the amount of compound a is greater than the amount of compound B and/or compound C.

According to an embodiment of the invention, the degreasing agent further comprises an organic solvent and/or water.

According to an embodiment of the invention, the degreaser comprises the following components in parts by weight:

20-70 parts of isomeric alcohol block polyether;

1-15 parts of an organic solvent;

20-60 parts of water;

the isomeric alcohol block polyether comprises three isomeric alcohol block polyethers with different HLB values; preferably, compound C having compound B, HLB value of greater than 13 and equal to or less than 15 with compound A, HLB value between 8 and 11 HLB value greater than 11 and equal to or less than 13.

According to an embodiment of the invention, the compound a is present in an amount of 20-30 parts, for example 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 parts.

According to an embodiment of the invention, the compound B is present in an amount of 5-15 parts, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 parts.

According to an embodiment of the invention, said compound C is present in an amount of 5-15 parts, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 parts.

According to an embodiment of the invention, the organic solvent is present in an amount of 5-10 parts, such as 5, 6, 7, 8, 9, 10 parts.

According to the embodiment of the invention, the organic solvent is one or a mixture of more than two of ethylene glycol, propylene glycol, ethylene glycol monobutyl ether and isopropanol.

According to an embodiment of the invention, the water is present in an amount of 30-50 parts, such as 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 parts.

According to an embodiment of the invention, the degreasing agent may optionally further comprise a biocide.

When present, the fungicide may be present in an amount of 0.01 to 0.2 parts by weight, such as 0.05 to 0.1 parts, for example 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1 parts.

According to an embodiment of the invention, the bactericidal agent may be morpholine and/or benzisothiazolinone.

According to an embodiment of the invention, the sum of the parts by weight of the components in the degreaser is 100 parts.

The invention also provides a preparation method of the degreasing agent, which comprises the step of uniformly mixing all the components. Preferably, the components are uniformly mixed according to the weight parts.

The invention also provides a method for degreasing leather products, which comprises the step of contacting the leather products with the degreasing agent.

The invention also provides a method for reducing the grease content of leather or leather, which comprises the step of contacting the leather with the degreasing agent.

The invention also provides application of the degreasing agent in leather goods degreasing. For example for degreasing after immersion in water and/or degreasing after softening. For example, for use in degreasing the interior of leather goods.

The leather piece is a hide, preferably an animal hide, such as cow hide, sheep hide or pig hide.

The invention also provides leather comprising one, two, three or more of the isomeric alcohol block polyethers. Preferably, the leather comprises leather pieces processed by the isomeric alcohol block polyether.

Preferably, the leather is prepared from the leather goods, for example by degreasing the leather goods.

The invention has the beneficial effects that:

the degreasing agent containing the isomeric alcohol block polyethers with different HLB values, provided by the invention, has good permeation and emulsification effects, and the isomeric alcohol block polyethers with low HLB value elute the grease in the leather interior to the outside, and are emulsified by the surfactant with high HLB value, so that the effect of high-efficiency degreasing is achieved, and the grease content in the leather embryo can be effectively reduced. Meanwhile, the nonionic surfactant is used as the main component, so that the influence of the ionic property on the combination of the subsequent material and the leather is avoided. The fatting agent is suitable for processing and degreasing animal skins or leather pieces such as cow skins, sheep skins, pigskins and the like.

The degreasing agent provided by the invention can replace a leather degreasing agent containing an anionic surfactant and a part of nonionic surfactant, and can increase the cleaning rate of grease and reduce the problems caused by grease residue on the basis of not influencing the combination of subsequent materials and leather.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

Parts, amounts in the context of the present invention are parts by weight, amounts by weight, unless otherwise indicated.