CN111763780A - Leather degreasing agent and preparation method and application thereof - Google Patents
Leather degreasing agent and preparation method and application thereof Download PDFInfo
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- CN111763780A CN111763780A CN202010544888.0A CN202010544888A CN111763780A CN 111763780 A CN111763780 A CN 111763780A CN 202010544888 A CN202010544888 A CN 202010544888A CN 111763780 A CN111763780 A CN 111763780A
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- 239000010985 leather Substances 0.000 title claims abstract description 70
- 239000013527 degreasing agent Substances 0.000 title claims abstract description 52
- 238000005237 degreasing agent Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 33
- 238000005238 degreasing Methods 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 11
- 241001494479 Pecora Species 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 14
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 10
- 229940126062 Compound A Drugs 0.000 claims description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003899 bactericide agent Substances 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- 230000000844 anti-bacterial effect Effects 0.000 claims description 5
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 241001465754 Metazoa Species 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 210000001161 mammalian embryo Anatomy 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000004945 emulsification Methods 0.000 abstract description 2
- 239000004519 grease Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 102000004882 Lipase Human genes 0.000 description 3
- 108090001060 Lipase Proteins 0.000 description 3
- 239000004367 Lipase Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- 235000019421 lipase Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C5/00—Degreasing leather
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
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 ]2CH(CH3)O]n(CH2CH2O)mH (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.
Description
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 C5-20At least one of the isomeric alkyl radicals, for example, may be C8-14At 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 C1-6Such 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.
Example 1
The degreasing agent comprises the following components in percentage by weight:
the compound A is isomeric alcohol block polyether with a structure shown in a formula (1), and the HLB value of the compound A is 10.5.
The compound B is isomeric alcohol block polyether with the structure shown in the formula (2), and the HLB value of the compound B is 11.5.
The compound C is isomeric alcohol block polyether with the structure shown in the formula (3), and the HLB value of the compound C is 13.5.
The organic solvent is a mixture of ethylene glycol and ethylene glycol monobutyl ether in a mass ratio of 1: 1.
The bactericide is a mixture of morpholine and benzisothiazolinone according to the mass ratio of 1: 1.
The degreasing agent of the embodiment is prepared by uniformly mixing the components according to the proportion.
Example 2
The degreasing agent comprises the following components in percentage by weight:
compound a, compound B and compound C were the same as in example 1.
The solvent is a mixture of ethylene glycol and ethylene glycol monobutyl ether in a mass ratio of 1: 3.
The bactericide is morpholine and benzisothiazolinone.
The degreasing agent of the embodiment is prepared by uniformly mixing the components according to the proportion.
Example 3 a degreaser, comprising the following components in parts by weight:
the compound A is isomeric alcohol block polyether with a structure shown as a formula (4), and the HLB value of the compound A is 10.5.
The compound B is isomeric alcohol block polyether with the structure shown in the formula (5), and the HLB value of the compound B is 11.5.
The compound C is isomeric alcohol block polyether with the structure shown in the formula (6), and the HLB value of the compound C is 13.5.
The solvent is a mixture of ethylene glycol and ethylene glycol monobutyl ether in a mass ratio of 1: 1.
The bactericide is a mixture of morpholine and benzisothiazolinone according to the mass ratio of 1: 1.
The degreasing agent of the embodiment is prepared by uniformly mixing the components according to the proportion.
Test example 1
The saline wet sheepskin was treated with the degreaser prepared in examples 1-3 as a method of degreasing treatment:
1. soaking in water and degreasing
(1) Putting the soaked skins into a rotary drum, taking the weight of the salt-wet skins as a material basis, adding 2 times of water of the salt-wet skins into the rotary drum, adding a degreasing agent accounting for 1% of the weight of the salt-wet skins at 35-37 ℃, rotating for 90min, and discharging liquid;
(2) adding water into the drum again, wherein the amount of the water is 2 times of the weight of the salt wet skins, rotating the drum at room temperature for 10min, and discharging the liquid after cleaning;
(3) and (3) after the step (2) is finished, taking out the leather, measuring the oil content in the leather embryo, comparing the oil content with the oil content in the leather embryo before the step (1), and detecting the degreasing capability of the high-efficiency degreasing agent.
2. Defatting after softening
(1) Putting the leather blank softened by the conventional method into a rotary drum, taking the weight of the gray leather as a material basis, adding 3% of degreasing agent into the softened leather blank after water control, and rotating for 45 min.
(2) Adding 30-35 deg.C water 1.5 times the weight of the ash into the rotary drum, rotating for 20min, and discharging liquid.
(3) Adding water into the drum again, wherein the amount of the water is 2 times of the weight of the blue, rotating at room temperature for 10min, and discharging the liquid after cleaning;
(4) and (4) repeating the operation in the step (3).
(5) And (4) after the step (4) is finished, taking out the leather, measuring the oil content in the leather embryo, comparing the oil content with the oil content in the leather embryo before the step (1), and detecting the degreasing capability of the degreasing agent in the embodiment 1.
3. According to the above method, the leather samples obtained by treating the degreasing agent of example 1 with water without a degreasing agent as a blank group, replacing both compounds B and C in the degreasing agent of example 1 with compound a (50% by mass of compound a, calculated as sample 4), replacing both compounds a and C in the degreasing agent of example 1 with compound B (50% by mass of compound B, calculated as sample 5), replacing both compounds a and B in the degreasing agent of example 1 with compound C (50% by mass of compound C, calculated as sample 6), and treating the commercial anionic degreasing agent (type Tergolix D, Clariant) were used as a control group.
The oil content of the leather sample before and after each performance treatment is detected according to the method of GB/T22933-2008 leather and fur chemical test determination of free fatty acid, and the test results are shown in Table 1.
TABLE 1
The experimental results show that: when the sample 4 is subjected to degreasing test, grease cannot be emulsified after being separated, and massive grease floats on the surface of bath solution, so that a large amount of grease adheres to the surface of the skin when the skin is taken out, and the degreasing requirement cannot be met. When samples 5 and 6 were used, the grease after removal was completely emulsified and no grease was adhered, but the grease removal effect was worse than that of sample 4 due to its poor permeability. The degreasing agents prepared in examples 1 to 3 do not have the above-mentioned drawbacks and have more excellent degreasing effects.
Test example 2
The softened and degreased sheepskins treated with the commercial samples of example 1 and test example 1 were tanned according to a general aldehyde tanning process as follows:
putting the treated skin into a rotary drum, adding water 2 times the weight of the skin, adding a fat-liquoring agent (GLH fat-liquoring agent, Bomei company) 3% of the weight of the skin at 30-35 ℃, rotating for 30min, and detecting the pH value of the solution in the rotary drum, wherein the pH value is required to be 3.0-3.5;
(2) adding a glutaraldehyde aqueous solution with the tare weight of 3% (the concentration of glutaraldehyde is 25 wt%) into the rotary drum, and rotating for 4 h;
(3) and (3) after the step (2) is finished, adding 10mL of 10 wt% sodium carbonate aqueous solution into the rotary drum every 1h, detecting the pH of the solution before each addition, wherein the pH of the solution is required to be 6.0-6.3, rotating for 1h after the addition is finished, taking out the rotary drum, washing for 10min, hanging, airing and drying.
(4) The shrinkage temperature was measured according to QB/T2713-2005 method for measuring shrinkage temperature in leather physical and mechanical tests. The test results are shown in table 2.
TABLE 2
As can be seen from table 2, the degreaser prepared in example 1 did not affect the bonding of the subsequent materials to the leather compared to the commercially available anionic degreaser. And the commercial anionic degreasing agent is firstly combined with the amino in the collagen, so that the subsequent combination of glutaraldehyde and the amino is hindered, and the shrinkage temperature of the finished leather is reduced compared with that of the leather sample of the unaffected example 1.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
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 C5-20At least one of the isomeric alkyl radicals, preferably C8-14At 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 C1-6Linear 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.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101027415A (en) * | 2004-08-30 | 2007-08-29 | 克莱里安特财务(Bvi)有限公司 | Process and compositions for wet degreasing of pelts, skins, hides, leather intermediate products and non-finished leather |
| CN101831362A (en) * | 2010-06-10 | 2010-09-15 | 中国皮革和制鞋工业研究院 | High efficiency low-foaming blue leather degreaser |
| CN108384645A (en) * | 2018-01-31 | 2018-08-10 | 佛山科富科技有限公司 | Workpiece degreasing agent, preparation method and workpiece surface spray soak method |
| CN110452369A (en) * | 2019-07-04 | 2019-11-15 | 联泓(江苏)新材料研究院有限公司 | A kind of isomerized alcohol block polyether and its preparation method and application that oil removing emulsifiability is excellent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101027415A (en) * | 2004-08-30 | 2007-08-29 | 克莱里安特财务(Bvi)有限公司 | Process and compositions for wet degreasing of pelts, skins, hides, leather intermediate products and non-finished leather |
| CN101831362A (en) * | 2010-06-10 | 2010-09-15 | 中国皮革和制鞋工业研究院 | High efficiency low-foaming blue leather degreaser |
| CN108384645A (en) * | 2018-01-31 | 2018-08-10 | 佛山科富科技有限公司 | Workpiece degreasing agent, preparation method and workpiece surface spray soak method |
| CN110452369A (en) * | 2019-07-04 | 2019-11-15 | 联泓(江苏)新材料研究院有限公司 | A kind of isomerized alcohol block polyether and its preparation method and application that oil removing emulsifiability is excellent |
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