CN102162015A - Comb-shaped amphiphilic modified styrene-maleic anhydride (SMA) tanning agent and preparation method thereof - Google Patents
Comb-shaped amphiphilic modified styrene-maleic anhydride (SMA) tanning agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a comb-shaped amphiphilic modified styrene-maleic anhydride (SMA) tanning agent and a preparation method thereof. SMA is subjected to esterification modification by using fatty alcohol and polyethylene glycol monomethyl ether to form the comb-shaped amphiphilic modified SMA tanning agent; and a lipophilic long-chain alkyl group, a hydrophilic ethyoxyl group and a hydrophilic carboxyl group are synchronously introduced into a molecular structure of the tanning agent. Original performance advantages of an SMA tanning agent are kept, and the tanning agent also overcomes the disadvantages of hard handfeel, easiness in color loss, low leveling property, no electrolyte resistance and the like when the using amount of the SMA tanning agent is large in retanning and fatliquoring of tanning. Therefore, the tanning agent is a functional material which integrates retanning, filling and fatliquoring into a whole, can endow finished leather with high elasticity, plump performance and fatliquoring performance, and has broader application prospect in the tanning industry.
Description
Technical field
The present invention relates to the leather chemicals production field, be specifically related to SMA tanning agent of a kind of comb shape amphiphilic modification and preparation method thereof.
Background technology
1945, Alfey and Lavin started the beginning of styrene-maleic anhydride copolymer (SMA) research.Afterwards, Mayo has carried out systematic research to the phenylethylene-maleic anhydride copolymerization system, thinks that this system copolymerization product is a kind of typical alternating copolymer.So far, the preparation of SMA and the research of application more and more are subject to people's attention.
At home, Zhang Juxian etc. are applied to process hides the earliest with the sodium salt (SMA tanning agent or KS-1 synthetic tanning agent) of SMA, careful through its tanned crust leather grain, pore is clear, and the leather body is plentiful, the yield of leather height, have and significantly brighten thickening characteristics, be particularly suitable for producing white and remove from office and the light color leather, chromium is also had absorption, fixed action, can reduce the chromium content in the waste liquid, reduce environmental pollution.Its related products also has the DLT-14 synthetic tanning agent, PR-1 retanning agent product of Renektan QS, Dandong light industry research institute development of French Kuhlman Corp. (US) 2565 West Maple Road, Troy, Michigan 48084, United States of etc.So the polymkeric substance of SMA based structures has comparatively widely at leather industry as retanning agent to be used always.
But the sodium salt of SMA early also has fatal shortcoming as retanning agent.Material styrene is the stronger monomer of rigidity, and its multipolymer second-order transition temperature is higher, can cause leather hand feeling harder after the retanning; Contain a large amount of carboxyls in this SMA tanning agent molecule, the leather fiber negatively charged ion is electrically strengthened, can influence the dyeing of later stage leather, easily produce the phenomenon of losing colour, make dyeing inhomogeneous, not bright-coloured.
In recent years, many process hides workers concentrated on the study on the modification work to the SMA tanning agent on the anhydride group on the molecular backbone chain.Because the ring molecule of maleic anhydride contains carbon-carbon double bond and carbonyl conjugated structure, reactive behavior is very high, can carry out addition reaction, Diels-Alder reaction, esterification, amidate action etc.Therefore, utilize the principle that the unitary anhydride group of maleic anhydride and chemical compound lot can carry out graft modification among the SMA, can form many SMA derivatives,, mainly contain following research about the SMA derivative and in the research aspect the leather tanning with value:
(preparation and the application performance thereof of SMA aliphatic alcohol monoesters sodium salt such as Li Xiaohua, Chinese leather .2009,3(38): 40 ~ 43.) SMA is carried out esterification modification, prepared the high fatty alcohol monoesters of SMA with Fatty Alcohol(C12-C14 and C12-C18) (lauryl alcohol, tetradecyl alcohol, hexadecanol or stearyl alcohol).This product back finished leather better softness of tanning, this method have been improved the harder shortcoming of leather hand feeling after the SMA retanning, but the wetting ability of this product is not strong, and emulsion dispersion property is not good, and emulsification is difficulty comparatively, has influenced retanning stuffing effect.
Zhang Fulian, (synthesizing of toxilic acid castor-oil plant alcohol ester-styrol copolymer such as Zhang Xilan, print during chemical industry. 2003,6(17): be that raw material is by the synthetic toxilic acid castor-oil plant alcohol of esterification monoesters with ricinoleic acid and maleic anhydride earlier 28 ~ 30.), carry out free-radical polymerized with vinylbenzene again, prepare a kind of tanning agent that has retanning, filling, stuffing and help the effect of dying after the modification, this product is also given characteristics such as finished leather softness, plentiful, level dyeing, waterproof except that the advantage that keeps the SMA tanning agent.
Summary of the invention
SMA tanning agent of and a kind of modification that provide not enough in performance aspect leather retanning, the stuffing at existing research product and preparation method thereof is provided.Main thought is: adopt Fatty Alcohol(C12-C14 and C12-C18) and poly glycol monomethyl ether that SMA is carried out common esterification modification, on the SMA molecular backbone chain after the modification, introduce chain alkyl, can effectively reduce the frictional coefficient between the collegen filament after the retanning, leather fiber is had lubricated submissive effect, finally play the stuffing effect; In addition, on this molecular backbone chain, introduce hydrophilic oxyethyl group again, can effectively improve water-soluble, the acidproof and electrolyte-resistant performance of SMA tanning agent after the modification.SMA tanning agent molecular chain after its modification is comb shaped structure, also has hydrophilic and two kinds of chemical groups of oleophylic on the side chain simultaneously, makes this polymkeric substance have amphipathic constitutional features, also belongs to a kind of comb polymer molecule tensio-active agent.
In order to achieve the above object, the technical solution used in the present invention is:
The Molecular Structure Design of the SMA tanning agent of a kind of comb shape amphiphilic modification is schematically as follows:
In the formula: M represents Na
+, K
+, NH
4 +, HOCH
2CH
2NH
3 +, (HOCH
2CH
2)
2NH
2 +, (HOCH
2CH
2)
3NH
+One of; R represents chain alkyl (C
12~ C
18); M represents the number of oxyethyl group; N represents the polymerization degree.
The preparation method of the SMA tanning agent of above-mentioned comb shape amphiphilic modification carries out esterification modification with Fatty Alcohol(C12-C14 and C12-C18) and poly glycol monomethyl ether jointly to SMA, makes the SMA tanning agent of comb shape amphiphilic modification.
This method may further comprise the steps:
The first step, get the poly glycol monomethyl ether of the Fatty Alcohol(C12-C14 and C12-C18) of the SMA of 202 parts of mass fractions, 46.5 ~ 202.5 parts of mass fractions, 62.5 ~ 900 parts of mass fractions and the catalyzer of 2.0 ~ 5.9 parts of mass fractions, above-mentioned reactant is joined in the reactor that has agitator, thermometer and condensing works, 2 ~ 4 times the organic solvent that adds reaction-ure mixture, react 2 ~ 4h down at 80 ~ 100 ℃, organic solvent is removed in underpressure distillation.
In second step, being neutralized to reaction system pH with alkaline aqueous solution (concentration is 20%~30%) is 6.0 ~ 7.0, and adjusting product solids content is 20 ~ 40% to get final product.
It is 1000 ~ 10000 SMA that described SMA selects average molecular mass for use, and its structural formula is:
In the formula: n
1The expression polymerization degree.
Described Fatty Alcohol(C12-C14 and C12-C18) is lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, C
12~ C
14, C
16~ C
18One of alcohol mixture.
Described poly glycol monomethyl ether is one of MPEG-250, MPEG-550, MPEG-600, MPEG-750, MPEG-1000, MPEG-1200.
Described organic solvent is the DMF(N-methylformamide), one of DMSO(dimethyl sulfoxide (DMSO)), diox, butanone.
Described catalyzer is tosic acid or sulfuric acid.
The alkali of described alkaline aqueous solution is one of NaOH, KOH, ammoniacal liquor, Monoethanolamine MEA BASF, diethanolamine, trolamine aqueous solution.
The present invention has the following advantages:
1, contains carboxyl and chain alkyl simultaneously in the SMA molecule of the comb shape amphiphilic modification of present method preparation.This product has good retanning, stuffing performance, can be widely used in the retanning of broad variety crust leathers such as pig, ox, sheep.
2, the oxyethyl group that has some amount in the SMA molecular structure of the comb shape amphiphilic modification of present method preparation can improve water-soluble, the acidproof and electrolyte-resistant performance of this tanning agent.
Modification work of the present invention has the not available advantage of other method of modifying at present, not only keep SMA tanning agent inherent filling properties, but also improved the insufficient shortcoming of crust leather flexibility after the retanning of SMA tanning agent, simultaneously, SMA tanning agent after the modification has excellent wetting ability, emulsifying dispersivity is good, and seepage force is strong, has excellent retanning stuffing performance, plentiful, soft, the good springiness of crust leather leather body after the retanning, tensile strength and tear strength all increase.
Embodiment
Below by embodiment the present invention is specifically described.
Embodiment 1
The first step, get the poly glycol monomethyl ether of the Fatty Alcohol(C12-C14 and C12-C18) of the SMA of 202 parts of mass fractions, 139.5 parts of mass fractions, 62.5 parts of mass fractions and the catalyzer of 2.0 parts of mass fractions, above-mentioned reactant is joined in the reactor that has agitator, thermometer and condensing works, 2.5 times the organic solvent that adds reaction-ure mixture, react 3h down at 85 ℃, underpressure distillation removes to desolvate and obtains reaction product.Described SMA average molecular mass is 2000; Described Fatty Alcohol(C12-C14 and C12-C18) is a lauryl alcohol; Described poly glycol monomethyl ether is MPEG-250; Described organic solvent is a diox; Described catalyzer is a tosic acid.
In second step, being neutralized to reaction system pH with 20% alkaline aqueous solution is 7.0, and adjusting product solids content is 30% to get final product.The alkali of described alkaline aqueous solution is NaOH.
Embodiment 2
The first step, get the poly glycol monomethyl ether of the Fatty Alcohol(C12-C14 and C12-C18) of the SMA of 202 parts of mass fractions, 140 parts of mass fractions, 75 parts of mass fractions and the catalyzer of 2.1 parts of mass fractions, above-mentioned reactant is joined in the reactor that has agitator, thermometer and condensing works, 2.5 times the organic solvent that adds reaction-ure mixture, react 3.5h down at 80 ℃, underpressure distillation removes to desolvate and obtains reaction product.Described SMA average molecular mass is 4000; Described Fatty Alcohol(C12-C14 and C12-C18) is C
12~ C
14Alcohol mixture; Described poly glycol monomethyl ether is MPEG-250; Described organic solvent is a butanone; Described catalyzer is a tosic acid.
In second step, being neutralized to reaction system pH with 20% alkaline aqueous solution is 6.5, and adjusting product solids content is 25% to get final product.The alkali of described alkaline aqueous solution is ammoniacal liquor.
Embodiment 3
The first step, get the poly glycol monomethyl ether of the Fatty Alcohol(C12-C14 and C12-C18) of the SMA of 202 parts of mass fractions, 107 parts of mass fractions, 275 parts of mass fractions and the catalyzer of 2.9 parts of mass fractions, above-mentioned reactant is joined in the reactor that has agitator, thermometer and condensing works, 3 times the organic solvent that adds reaction-ure mixture, react 3h down at 90 ℃, underpressure distillation removes to desolvate and obtains reaction product.Described SMA average molecular mass is 3000; Described Fatty Alcohol(C12-C14 and C12-C18) is a tetradecyl alcohol; Described poly glycol monomethyl ether is MPEG-550; Described organic solvent is DMSO; Described catalyzer is a sulfuric acid.
In second step, being neutralized to reaction system pH with 20% alkaline aqueous solution is 7.0, and adjusting product solids content is 35% to get final product.The alkali of described solution is KOH.
Embodiment 4
The first step, get the poly glycol monomethyl ether of the Fatty Alcohol(C12-C14 and C12-C18) of the SMA of 202 parts of mass fractions, 60.5 parts of mass fractions, 450 parts of mass fractions and the catalyzer of 3.6 parts of mass fractions, above-mentioned reactant is joined in the reactor that has agitator, thermometer and condensing works, 2 times the organic solvent that adds reaction-ure mixture, react 3h down at 95 ℃, underpressure distillation removes to desolvate and obtains reaction product.Described SMA average molecular mass is 6000; Described Fatty Alcohol(C12-C14 and C12-C18) is a hexadecanol; Described poly glycol monomethyl ether is MPEG-600; Described organic solvent is DMF; Described catalyzer is a sulfuric acid.
In second step, being neutralized to reaction system pH with 30% alkaline aqueous solution is 6.5, and adjusting product solids content is 40% to get final product.The alkali of described alkaline aqueous solution is trolamine.
Embodiment 5
The first step, get the poly glycol monomethyl ether of the Fatty Alcohol(C12-C14 and C12-C18) of the SMA of 202 parts of mass fractions, 128 parts of mass fractions, 375 parts of mass fractions and the catalyzer of 3.5 parts of mass fractions, above-mentioned reactant is joined in the reactor that has agitator, thermometer and condensing works, 2.5 times the organic solvent that adds reaction-ure mixture, react 4h down at 85 ℃, underpressure distillation removes to desolvate and obtains reaction product.Described SMA average molecular mass is 8000; Described Fatty Alcohol(C12-C14 and C12-C18) is C
16~ C
18Alcohol mixture; Described poly glycol monomethyl ether is MPEG-750; Described organic solvent is a diox; Described catalyzer is a tosic acid.
In second step, being neutralized to reaction system pH with 30% alkaline aqueous solution is 6.0, and adjusting product solids content is 25% to get final product.The alkali of described alkaline aqueous solution is diethanolamine.
Embodiment 6
The first step, get the poly glycol monomethyl ether of the Fatty Alcohol(C12-C14 and C12-C18) of the SMA of 202 parts of mass fractions, 102.4 parts of mass fractions, 600 parts of mass fractions and the catalyzer of 4.5 parts of mass fractions, above-mentioned reactant is joined in the reactor that has agitator, thermometer and condensing works, 3.5 times the organic solvent that adds reaction-ure mixture, react 3h down at 90 ℃, underpressure distillation removes to desolvate and obtains reaction product.Described SMA average molecular mass is 10000; Described Fatty Alcohol(C12-C14 and C12-C18) is C
16~ C
18Alcohol mixture; Described poly glycol monomethyl ether is MPEG-1000; Described organic solvent is DMF; Described catalyzer is a sulfuric acid.
In second step, being neutralized to reaction system pH with 30% alkaline aqueous solution is 7.0, and adjusting product solids content is 35% to get final product.The alkali of described alkaline aqueous solution is Monoethanolamine MEA BASF.
Embodiment 7
The first step, get the poly glycol monomethyl ether of the Fatty Alcohol(C12-C14 and C12-C18) of the SMA of 202 parts of mass fractions, 135 parts of mass fractions, 500 parts of mass fractions and the catalyzer of 4.2 parts of mass fractions, above-mentioned reactant is joined in the reactor that has agitator, thermometer and condensing works, 4 times the organic solvent that adds reaction-ure mixture, react 2.5h down at 100 ℃, underpressure distillation removes to desolvate and obtains reaction product.Described SMA average molecular mass is 7000; Described Fatty Alcohol(C12-C14 and C12-C18) is a stearyl alcohol; Described poly glycol monomethyl ether is MPEG-1000; Described organic solvent is DMSO; Described catalyzer is a tosic acid.
In second step, being neutralized to reaction system pH with 20% alkaline aqueous solution is 6.0, and adjusting product solids content is 30% to get final product.The alkali of described alkaline aqueous solution is KOH.
Embodiment 8
The first step, get the poly glycol monomethyl ether of the Fatty Alcohol(C12-C14 and C12-C18) of the SMA of 202 parts of mass fractions, 67.5 parts of mass fractions, 900 parts of mass fractions and the catalyzer of 5.8 parts of mass fractions, above-mentioned reactant is joined in the reactor that has agitator, thermometer and condensing works, 3 times the organic solvent that adds reaction-ure mixture, react 3h down at 90 ℃, underpressure distillation removes to desolvate and obtains reaction product.Described SMA average molecular mass is 5000; Described Fatty Alcohol(C12-C14 and C12-C18) is a stearyl alcohol; Described poly glycol monomethyl ether is MPEG-1200; Described organic solvent is a diox; Described catalyzer is a sulfuric acid.
In second step, being neutralized to reaction system pH with 20% alkaline aqueous solution is 7.0, and adjusting product solids content is 25% to get final product.The alkali of described alkaline aqueous solution is ammoniacal liquor.
Present embodiment only is used for the present invention is further detailed, and can not be interpreted as the restriction of protection domain, the person skilled in the art of this area according to the present invention content make some nonessential improvement and adjust and also belong to protection scope of the present invention.
Claims (9)
1. the SMA tanning agent of comb shape amphiphilic modification is characterized in that, the structure of this tanning agent as shown in the formula:
In the formula: M represents Na
+, K
+, NH
4 +, HOCH
2CH
2NH
3 +, (HOCH
2CH
2)
2NH
2 +, (HOCH
2CH
2)
3NH
+One of; R represents chain alkyl (C
12~ C
18); M represents the number of oxyethyl group; N represents the polymerization degree.
2. the preparation method of the described comb shape amphiphilic of claim 1 modification SMA tanning agent carries out esterification modification with Fatty Alcohol(C12-C14 and C12-C18) and poly glycol monomethyl ether to SMA, makes the SMA tanning agent of comb shape amphiphilic modification.
3. the SMA tanning agent preparation method of comb shape amphiphilic according to claim 2 modification is characterized in that this method may further comprise the steps:
The first step, get the poly glycol monomethyl ether of the Fatty Alcohol(C12-C14 and C12-C18) of the SMA of 202 parts of mass fractions, 46.5 ~ 202.5 parts of mass fractions, 62.5 ~ 900 parts of mass fractions and the catalyzer of 2.0 ~ 5.9 parts of mass fractions, above-mentioned reactant is joined in the reactor that has agitator, thermometer and condensing works, 2 ~ 4 times the organic solvent that adds reaction-ure mixture, react 2 ~ 4h down at 80 ~ 100 ℃, organic solvent is removed in underpressure distillation;
Second step, with concentration be 20%~30% alkaline aqueous solution to be neutralized to reaction system pH be 6.0 ~ 7.0, adjusting product solids content is 20 ~ 40% to get final product.
5. the preparation method of the SMA tanning agent of comb shape amphiphilic according to claim 2 modification is characterized in that, described Fatty Alcohol(C12-C14 and C12-C18) is lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, C
12~ C
14, C
16~ C
18One of alcohol mixture.
6. the preparation method of the SMA tanning agent of comb shape amphiphilic according to claim 2 modification, it is characterized in that described poly glycol monomethyl ether (MPEG) is one of MPEG-250, MPEG-550, MPEG-600, MPEG-750, MPEG-1000, MPEG-1200.
7. the preparation method of the SMA tanning agent of comb shape amphiphilic according to claim 2 modification is characterized in that, described organic solvent is the DMF(N-methylformamide), one of DMSO(dimethyl sulfoxide (DMSO)), diox, butanone.
8. the preparation method of the SMA tanning agent of comb shape amphiphilic according to claim 2 modification is characterized in that, described catalyzer is tosic acid or sulfuric acid.
9. the preparation method of the SMA tanning agent of comb shape amphiphilic according to claim 2 modification is characterized in that, the alkali of described alkaline aqueous solution is one of NaOH, KOH, ammoniacal liquor, Monoethanolamine MEA BASF, diethanolamine, trolamine aqueous solution.
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CN114369183A (en) * | 2021-11-30 | 2022-04-19 | 兄弟科技股份有限公司 | Cationization modified SMA retanning agent and preparation method thereof |
CN114736381A (en) * | 2022-04-20 | 2022-07-12 | 无锡颐景丰科技有限公司 | Comb-shaped high-molecular surfactant and synthesis method thereof |
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Application publication date: 20110824 |