CN1526833A - Composite leather greasing agent and its prepn process - Google Patents

Composite leather greasing agent and its prepn process Download PDF

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Publication number
CN1526833A
CN1526833A CNA031390692A CN03139069A CN1526833A CN 1526833 A CN1526833 A CN 1526833A CN A031390692 A CNA031390692 A CN A031390692A CN 03139069 A CN03139069 A CN 03139069A CN 1526833 A CN1526833 A CN 1526833A
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China
Prior art keywords
composite leather
add
agent
fatting agent
oil
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CNA031390692A
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CN1229504C (en
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辛寅昌
侯尔群
徐俊
安骏
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Shandong University
Shandong Normal University
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Shandong Normal University
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Abstract

The present invention belongs to the field of leather chemical technology. The composite leather greasing agent is prepared with polyoxyethylene alkyl phosphate, cottonseed oil amide, chlorinated paraffin, octyl phenol polyethenoxy ether, sodium alkylsulfate, olive oil glycolate and No. 30 engine oil. The preparation process includes mixing, heating and other steps. The composite leather greasing agent makes leather soft, tough, plumpy, elastic, waterproof, silky, good in stuffing performance, stable in quality and infrared and ultraviolet resistant, and has low cost. The composite leather greasing agent is suitable for cow skin, sheep skin and pig skin.

Description

A kind of composite leather fatting agent and preparation method thereof
(1) technical field
The present invention relates to a kind of NEW TYPE OF COMPOSITE leather fat that is applicable to that ox-hide, sheepskin, pigskin stuffing are used, belong to the leather chemical industry technical field.
(2) background technology
Be processed in the process of leather at the natural animal skin, high-grade leather fat should possess and have toughness in the leather of the making softness, have elasticity in plentiful, has the smooth finish of silk fabrics, waterproof, the irradiation of anti-infrared and UV-light, not stiff rotten performance with the variation of weather and time.In addition, leather fat itself also should possess and is easy to be absorbed by leather, behind the leather greasing in the waste liquid raffinate amount few, performance such as biological degradability is good.Therefore, a kind of compound leather greasing agent prescription that has above various performances concurrently has been subjected to attention both domestic and external.Chinese patent application numbers 88106317 discloses the preparation of fatty amide yl carboxylic acid sodium composite leather fat, it is that the main composite sulfation lard, clorafin, alkylsulphonic acid ammonium gone up is formed by fatty amide yl carboxylic acid sodium, and this application claims fat liquoring complex agent stuffing effect, filling properties good.Chinese patent application number 93108780 disclosed leather fats are to be main by sulfonated vegetable oil, with clorafin, fullness imparting fish oil, chlorination lard, rape oil, rape oil fat and polyoxyethylene ester with peregal is composite forms, this fatting agent becomes grain careful according to reports, pore is clear, elastomeric flexible, straight and even smooth, good hand feeling, the leather oil-containing focuses between 12~24%.Chinese patent application numbers 99115091 discloses ammonium chloride phosphoric acid fat leather fat and preparation method, and it is made up of ammonium chloride phosphoric acid fat leather fat, the trimethyl carbinol and water, and this invention belongs to zwitterionics and is used for leather greasing.More than the technology that provides of disclosed patent application be to adopt tensio-active agent and grease physics composite, in water, form milk sap, its shortcoming is that the thermodynamic stability of fatting agent is undesirable.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of microemulsion composite leather fatting agent new, that performance is more superior and preparation method thereof is provided.
Composite leather fatting agent of the present invention, it is composed as follows, is weight part:
The set of dispense ratio
Polyxyethylated phosphoesterase 30~100
Cottonseed oil amide 140~200
Clorafin 77~150
Polyoxyethylene octylphenol ether (TX-10) 10~60
Alkyl sodium sulfonate 40~150
The sweet oil macrogol ester, molecular weight 400~2,400 0~550
30 #Machine oil 0~470
Above-mentioned clorafin is 52 #Clorafin.
The alkyl of abovementioned alkyl sodium sulfonate is dodecyl, hexadecyl or 12~18 mixed alkyls.
Other above-mentioned components can be used commercially available finished product material.Also can use following method to prepare voluntarily and get:
1. the preparation of polyxyethylated phosphoric acid ester in synthesis reactor, adds fatty alcohol-polyoxyethylene ether, is heated to 40 ℃ then, and is even to fusing.Slowly add phosphorylation agent, the mol ratio of phosphorylation agent and fatty alcohol-polyoxyethylene ether is 1: 3~50, and with adding with stirring, temperature is controlled under 70~90 ℃ of conditions reacted 6~7 hours, reaction solution is brown transparence, quantitatively adds alkali after being cooled to 40 ℃ to be neutralized to PH=7~8.
In the preparation of above-mentioned polyxyethylated phosphoric acid ester, described phosphorylation agent is Vanadium Pentoxide in FLAKES or phosphoryl chloride, and alkali is selected from NaOH, KOH, Monoethanolamine MEA BASF, diethanolamine or trolamine one of them or its combination.The preparation of above-mentioned polyxyethylated phosphoric acid ester is that mixed fatty alcohol with the Fatty Alcohol(C12-C14 and C12-C18) of 12~18 carbon of a mole or 12~18 carbon is as initiator, under base catalysis at 120 ℃~130 ℃, the oxyethane of 10~30 moles of addition copolymerization under the 0.5MPa condition.
2. the preparation of cottonseed oil amide, in synthesis reactor, count by weight, add 240~480 portions of Oleum Gossypii semens,, add 160~180 parts of diethanolamine after being heated to 40 ℃ with adding with stirring, after being warmed up to 150 ℃ ± 5 ℃, add 2.0~3.3 parts of KOH, keep 150 ℃ ± 5 ℃ to react 3 hours down, to the transparence brown liquid.Wherein Oleum Gossypii semen is industrial one-level dephenolization cottonseed oil, and diethanolamine is industrial one-level, and content should be more than 98%, and KOH is the industrial goods of content more than 80%.
3. the preparation of sweet oil macrogol ester, in synthesis reactor, meter adds 100~200 parts of sweet oil by weight; with adding, add 80~150 parts of polyoxyethylene glycol after being heated to 100 ℃, logical nitrogen protection with stirring; add 1~5 part of KOH, be warmed up to 280 ℃, reacted four hours.Sweet oil wherein is industrial one-level, and molecular weight polyethylene glycol wherein is 400~1200, and KOH wherein is the industrial goods more than 80%.
The preparation method of composite leather fatting agent of the present invention, according to above-mentioned amount ranges, polyxyethylated phosphoric acid ester and/or cottonseed oil amide under 40 ± 5 ℃ of conditions, are mixed, add clorafin and sweet oil macrogol ester finish or 30 that mix then #Machine oil is warming up to 50 ± 5 ℃, mixes, and adds polyoxyethylene octylphenol ether (TX-10) and alkyl sodium sulfonate then 40 ± 5 ℃ of following mixing and stirring.
Composite leather fatting agent of the present invention is the sweet oil or 30 after the modification of employing natural plant grease #Machine oil, clorafin (being synthetic neat's foot oil) are base oil, with polyxyethylated phosphoric acid ester and cottonseed oil amide mix with base oil under the certain temperature condition form compound milk sap after, use alkyl sodium sulfonate and polyoxyethylene octylphenol ether (TX-10) to make it in the aqueous solution, form stable transparence microemulsion again, thereby make its perviousness, sorbency and sorption amount better as the solubilising promoting agent.Fatting agent of the present invention can make to have toughness behind the leather greasing, has elasticity in plentiful in the softness, waterproof, and the surface presents the mercerising sense, and filling properties is good, steady quality, anti-infrared and UV-irradiation does not change with weather and time and dry rotten, with low cost.Composite leather fatting agent of the present invention be applicable to ox-hide, sheepskin and pigskin stuffing.
Composite leather fatting agent of the present invention is to disperse oil-soluble clorafin (having another name called synthetic neat's foot oil), sweet oil macrogol ester or/and 30 with polyxyethylated phosphoric acid ester and cottonseed oil amide as water soluble surfactant active's emulsification #Machine oil adds the composite leather fatting agent that TX-10 and alkyl sodium sulfonate solubilising form thermodynamically stable transparent micro emulsion again.
(4) embodiment
According to different leather character, can adopt different configuration proportions.Take all factors into consideration cost and effect, the special embodiment that proposes following composite leather fatting agent, but technical scheme of the present invention is not limited only to this.
Embodiment 1: the fatting agent that the lamb skin clothing leather is used
Set of dispense is than (parts by weight)
Polyxyethylated phosphoric acid ester 80
Cottonseed oil amide 120
52 #Clorafin 150
Sodium cetanesulfonate 40
Polyoxyethylene octylphenol ether (TX-10) 60
Sweet oil macrogol ester 550
The preparation method be polyxyethylated phosphoric acid ester and cottonseed oil amide under 40 ± 5 ℃ of conditions, mix, add clorafin and the sweet oil macrogol ester finish that mixes then, be warming up to 50 ± 5 ℃, mix, add TX-10 and alkyl sodium sulfonate then 40 ± 5 ℃ of following mixing and stirring.
Polyxyethylated phosphoric acid ester wherein prepares by following method: in synthesis reactor, quantitatively adds fatty alcohol-polyoxyethylene ether, is heated to 40 ℃ then, and even to fusing.Slowly add the phosphorylation agent Vanadium Pentoxide in FLAKES, the mol ratio of Vanadium Pentoxide in FLAKES and fatty alcohol-polyoxyethylene ether is 1: 5, and with adding with stirring, temperature is controlled under 70~90 ℃ of conditions reacted 6~7 hours.Reaction solution is brown transparence.Quantitatively add NaOH after being cooled to 40 ℃ and be neutralized to PH=7~8.
The preparation method of above-mentioned polyxyethylated phosphoric acid ester be mixed fatty alcohol with 12~18 carbon of a mole as initiator, under NaOH catalysis at 120 ℃~130 ℃, the oxyethane of 20 moles of addition copolymerization under the 0.5MPa condition.
Above-mentioned cottonseed oil amide prepares by following method: in synthesis reactor, add 360 portions of Oleum Gossypii semens by weight, with adding with stirring, add 100 parts of diethanolamine after being heated to 40 ℃, after being warmed up to 150 ℃ ± 5 ℃, add 2.4 parts of KOH, keep 150 ℃ ± 5 ℃ to react 3 hours down, to the transparence brown liquid.Wherein Oleum Gossypii semen is industrial one-level dephenolization cottonseed oil, and diethanolamine is industrial one-level, and content is more than 98%, and KOH is the industrial goods of content more than 80%.
Above-mentioned sweet oil macrogol ester prepares by following method: in synthesis reactor, by weight, add 132 parts of sweet oil; with adding, add 80 parts of polyoxyethylene glycol when being heated to 100 ℃, logical nitrogen protection with stirring; add 1.1 parts of KOH, be warmed up to 280 ℃, reacted four hours.Sweet oil wherein is industrial one-level, and molecular weight polyethylene glycol is 800, and KOH is the industrial goods more than 80%.
Embodiment 2: the pig leather for making garment fatting agent
Set of dispense is than (parts by weight)
Polyxyethylated phosphoric acid ester 60
Cottonseed oil amide 180
52 #Clorafin 90
Sodium laurylsulfonate 100
TX-10??????????????????????????????50
Sweet oil macrogol ester 70
30 #Machine oil 400
The preparation method of leather fat be polyxyethylated phosphoric acid ester and cottonseed oil amide under 40 ± 5 ℃ of conditions, mix, add clorafin and sweet oil macrogol ester finish and 30 that mix then #Machine oil is warming up to 50 ± 5 ℃, mixes, and adds TX-10 and alkyl sodium sulfonate then 40 ± 5 ℃ of following mixing and stirring.
The preparation of polyxyethylated phosphoric acid ester wherein, cottonseed oil amide and sweet oil macrogol ester is with embodiment 1.
Embodiment 3: ox-hide sofa artificial leather fatting agent
Set of dispense is than (parts by weight)
Polyxyethylated phosphoric acid ester 40
Cottonseed oil amide 140
52 #Clorafin 40
Sodium laurylsulfonate 40
TX-10??????????????????????????????80
The preparation method of leather fat be polyxyethylated phosphoric acid ester and cottonseed oil amide under 40 ± 5 ℃ of conditions, mix, add clorafin then, be warming up to 50 ± 5 ℃, mix, add TX-10 and alkyl sodium sulfonate then 40 ± 5 ℃ of following mixing and stirring.
Polyxyethylated phosphoric acid ester wherein prepares by following method: in synthesis reactor, quantitatively adds fatty alcohol-polyoxyethylene ether, is heated to 40 ℃ then, and even to fusing.Slowly add the phosphorylation agent phosphoryl chloride, the mol ratio of phosphoryl chloride and fatty alcohol-polyoxyethylene ether is 3: 50, and with adding with stirring, temperature is controlled under 70~90 ℃ of conditions reacted 6~7 hours.Reaction solution is brown transparence.Quantitatively add NaOH after being cooled to 40 ℃ and be neutralized to PH=7~8.All the other processing condition are all with embodiment 1.
The preparation of cottonseed oil amide is with embodiment 1 in the present embodiment.
Embodiment 4: the composite leather fatting agent
As described in embodiment 1, different is that the composite leather fatting agent is composed as follows:
Set of dispense is than (parts by weight)
Cottonseed oil amide 200
52 #Clorafin 140
Sodium cetanesulfonate 40
Polyoxyethylene octylphenol ether (TX-10) 60
Sweet oil macrogol ester 500.
Table 1 leather fat physical properties of the present invention and usage and effect
Lamb skin Pigskin Ox-hide
Relative density (20 ℃) ????0.89~0.91 ????0.89~0.91 ????0.89~0.91
PH value ????7.0~8.0 ????7.0~8.0 ????7.0~8.0
Stability of emulsion (1: 9 water miscible liquid, 24h) No oil slick No oil slick No oil slick
Character behind table 2 leather greasing
Lamb skin Pigskin Ox-hide Outward appearance
Contain grease (%) before unaged ????8.3 ????9.0 ????6.7 Even dyeing, the strong soft smooth of fillibility
Contain grease (%) after aging ????6.3 ????8.3 ????6.1 Even dyeing, the strong soft smooth of fillibility
Annotate: the senile experiment condition is infrared, ultraviolet lighting 1000 hours.
The summary of table 3 leather greasing process
Lamb skin Pigskin Ox-hide
The normal temperature washing (minute) ??15 ??15 ??15
Stuffing total amount (%) ??16 ??16 ??16
Water temperature (℃) ??60~65 ??60~65 ??60~65
Time in the drum (minute) ??70 ??60 ??90
Formic acid (%) ??1.5 ??1.5 ??1.5
Stuffing disposes Wash out drum, take horse and spend the night Wash out drum, take horse and spend the night Wash out drum, take horse and spend the night

Claims (9)

1. the composite leather fatting agent is characterized in that, and is composed as follows, is weight part:
The set of dispense ratio
Polyxyethylated phosphoesterase 30~100
Cottonseed oil amide 140~200
Clorafin 77~150
Polyoxyethylene octylphenol ether 10~60
Alkyl sodium sulfonate 40~150
The sweet oil macrogol ester, molecular weight 400~2,400 0~550
30 #Machine oil 0~470.
2. composite leather fatting agent as claimed in claim 1 is characterized in that described clorafin is 52 #Clorafin.
3. composite leather fatting agent as claimed in claim 1 is characterized in that, the alkyl of described alkyl sodium sulfonate is dodecyl, hexadecyl or 12~18 mixed alkyls.
4. composite leather fatting agent as claimed in claim 1, it is characterized in that, described polyxyethylated phosphoric acid ester is to prepare as follows and get: in synthesis reactor, add fatty alcohol-polyoxyethylene ether, be heated to 40 ℃ then, even to fusing, slowly add phosphorylation agent, the mol ratio of phosphorylation agent and fatty alcohol-polyoxyethylene ether is 1: 3~50, with adding with stirring, temperature is controlled under 70~90 ℃ of conditions reacted 6~7 hours, and reaction solution is brown transparence, quantitatively added alkali after being cooled to 40 ℃ to be neutralized to PH=7~8.
5. composite leather fatting agent as claimed in claim 4 is characterized in that, described phosphorylation agent is Vanadium Pentoxide in FLAKES or phosphoryl chloride,
6. composite leather fatting agent as claimed in claim 4 is characterized in that, alkali is selected from NaOH, KOH, Monoethanolamine MEA BASF, diethanolamine or trolamine one of them or its combination.
7. composite leather fatting agent as claimed in claim 1, it is characterized in that, described cottonseed oil amide is to get by following method preparation: in synthesis reactor, meter adds 240~480 portions of Oleum Gossypii semens by weight, with adding with stirring, add 160~180 parts of diethanolamine after being heated to 40 ℃, be warmed up to 150 ℃ ± 5 ℃ after, add 2.0~3.3 parts of KOH, keep 150 ℃ ± 5 ℃ to react 3 hours down, to the transparence brown liquid.
8. composite leather fatting agent as claimed in claim 1; it is characterized in that; described sweet oil macrogol ester is to get by following method preparation: in synthesis reactor, meter adds 100~200 parts of sweet oil by weight; with adding with stirring; add 80~150 parts of polyoxyethylene glycol after being heated to 100 ℃, logical nitrogen protection adds 1~5 part of KOH; be warmed up to 280 ℃, reacted 4 hours.
9. the preparation method of the described composite leather fatting agent of claim 1, it is characterized in that, polyxyethylated phosphoric acid ester and/or cottonseed oil amide under 40 ± 5 ℃ of conditions, are mixed, add the clorafin that mixes and sweet oil macrogol ester finish then or/and 30 #Machine oil is warming up to 50 ± 5 ℃, mixes, and adds polyoxyethylene octylphenol ether and alkyl sodium sulfonate then 40 ± 5 ℃ of following mixing and stirring.
CN 03139069 2003-09-25 2003-09-25 Composite leather greasing agent and its prepn process Expired - Fee Related CN1229504C (en)

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Application Number Priority Date Filing Date Title
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101760570A (en) * 2009-12-29 2010-06-30 温州大学 Composite leather greasing agent and preparation method thereof
CN101864500A (en) * 2010-06-24 2010-10-20 陕西科技大学 Amphoteric wool grease leather fatliquoring agent and preparation method thereof
CN101643802B (en) * 2008-08-28 2012-09-05 齐河力厚化工有限公司 Modified phospholipid composite fat liquor and preparation thereof
CN101696457B (en) * 2009-10-21 2012-10-03 陕西科技大学 Organic long-chain fluorine-alcohol modified ASA leather waterproof fat liquoring agent and preparation method thereof
CN102703623A (en) * 2012-06-11 2012-10-03 科凯精细化工(上海)有限公司 Novel greasing agent for synthetic leather and preparation method for novel greasing agent
CN103695578A (en) * 2013-12-30 2014-04-02 青昊环保科技(上海)有限公司 Leather water-proof curing agent and preparing method thereof
CN105886676A (en) * 2016-06-29 2016-08-24 宋春燕 Leather fatliquoring agent
CN106399599A (en) * 2016-09-14 2017-02-15 齐河力厚化工有限公司 Preparation method of micro-emulsion type synthetic fatliquor

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101643802B (en) * 2008-08-28 2012-09-05 齐河力厚化工有限公司 Modified phospholipid composite fat liquor and preparation thereof
CN101696457B (en) * 2009-10-21 2012-10-03 陕西科技大学 Organic long-chain fluorine-alcohol modified ASA leather waterproof fat liquoring agent and preparation method thereof
CN101760570A (en) * 2009-12-29 2010-06-30 温州大学 Composite leather greasing agent and preparation method thereof
CN101760570B (en) * 2009-12-29 2013-05-01 温州大学 Composite leather greasing agent and preparation method thereof
CN101864500A (en) * 2010-06-24 2010-10-20 陕西科技大学 Amphoteric wool grease leather fatliquoring agent and preparation method thereof
CN101864500B (en) * 2010-06-24 2013-01-30 陕西科技大学 Amphoteric wool grease leather fatliquoring agent and preparation method thereof
CN102703623A (en) * 2012-06-11 2012-10-03 科凯精细化工(上海)有限公司 Novel greasing agent for synthetic leather and preparation method for novel greasing agent
CN103695578A (en) * 2013-12-30 2014-04-02 青昊环保科技(上海)有限公司 Leather water-proof curing agent and preparing method thereof
CN105886676A (en) * 2016-06-29 2016-08-24 宋春燕 Leather fatliquoring agent
CN106399599A (en) * 2016-09-14 2017-02-15 齐河力厚化工有限公司 Preparation method of micro-emulsion type synthetic fatliquor
CN106399599B (en) * 2016-09-14 2018-04-17 齐河力厚化工有限公司 A kind of preparation method of microemulsion-type synthetic fat liquor

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