CN103146850A - Salt-free pickling-free amphoteric polymer chrome-free tanning agent - Google Patents
Salt-free pickling-free amphoteric polymer chrome-free tanning agent Download PDFInfo
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Abstract
The invention discloses a salt-free pickling-free amphoteric polymer chrome-free tanning agent which is characterized in that according to the salt-free pickling-free amphoteric polymer chrome-free tanning agent, firstly, organic amine and fatty aldehyde with active alpha-H undergo Mannich reaction, a Mannich base midbody with a formyl group is obtained, and then, after an allyl monomer with the formyl group is generated in the original position of the midbody, the midbody, the allyl monomer with a cation and allyl acid undergo free radical polymerization, and the salt-free pickling-free amphoteric polymer chrome-free agent is obtained. The salt-free pickling-free amphoteric polymer chrome-free tanning agent is a polymer tanning agent containing the formyl group and has certain filling capacity, tanning properties of the salt-free pickling-free amphoteric polymer chrome-free tanning agent are rival with the properties of an existing aldehydes tanning agent, molecular weight is large, when the salt-free pickling-free amphoteric polymer chrome-free tanning agent is in use, a leather blank is free of pickling, salt pollution in the follow-up processes can be eliminated, carboxyl and amino contained by the agent can further prompt absorption to follow-up finishing materials by the leather blank, and the whole quality of a leather is improved. According to preparation of the salt-free pickling-free amphoteric polymer chrome-free tanning agent, air pollution due to raw materials is avoided, chrome and NaCl pollution of a traditional tanning agent is avoided, processes are reduced, silicate consumption is reduced, and cost is reduced.
Description
Technical field
The invention belongs to the chrome-free tanning agent technical field for tan leather, fur, be specifically related to a kind of salt-free not pickling amphiphilic polymers chrome-free tanning agent.
Background technology
Chromic tanning is the process for tanning of leather industry dominate, but chrome tanning process to be the process hides process the easiest to one of operation of environment.Just contain 1300 tons of total chromium in the annual 1.4 hundred million tons of waste water that produce of China's curriery, cause sewage difficulty of governance up to standard quite large.In addition, also contain the NaCl of 30000～40000mg/L that pickling procedure brings in conventional chroming waste liquor, this is the major cause that causes the comprehensive wastewater chloride ion content to exceed standard.In today that environment protection is day by day emphasized and paid attention to, chromic tanning has been faced with stern challenge as main process for tanning.Implementing not pickling chrome-free tanning technique and can not only solve the problem of pollution of chromium from the source, can also alleviate neutral salt to the pollution of environment, is to realize cleaning one of gordian technique of process hides.
Implement the chrome-free tanning agent that not pickling chrome-free tanning technique must depend on excellent property.Existing chrome-free tanning agent comprises vegetable tanning agent, non-chromium metal tanning agents, aldehyde tanning agent etc., wherein take aldehyde tanning agent as main.And the aldehydes tanning agent mainly contains glutaraldehyde, modified glutaraldehyde, organic phosphonium salt and oxazolidine tanning agent.from applicable cases, glutaraldehyde tanning agent tanning color jaundice, be not suitable for tanning light color leather (Xie Changzhi, Yu Qinglong, Tian Yubin. the development of modified glutaraldehyde tanning agent GW-I. Chinese leather. 2002,31:4-6.), the modified glutaraldehyde tanning agent is according to its mechanism of modification, at the tannery Diazolidinyl Urea, cause that in leather goods, formaldehyde content exceeds standard, thereby the harm human consumer healthy (Zhou Hualong. Leather Chemicals. Beijing: China Light Industry Press, 2009:9-34,51-52.), organic phosphonium salt is the compound that belongs to methylol phosphine structure, this tanning agent also can discharge free formaldehyde in the tanning process, cause finished leather free formaldehyde (the Shao SX that exceeds standard, Shi KQ, Li Y, et al. Mechanism of chrome-free tanning with tetra-hydroxymethyl phosphonium chloride. Chinese Journal of Chemical Engineering. 2008, 16:446-450. Wang Xue river, Zhao Yu, Yuan Xuzheng, Deng. tannin extract and organic phosphine are in conjunction with the research of the goat leather for making garment process for tanning of tanning. Chinese leather. and 2009, 38:4-7.), and the waste water of discharging also may eutrophication, thereby make water quality deterioration, the oxazolidine tanning agent not only also exists the problem that free formaldehyde exceeds standard, and such tanning agent belongs to the foreign patent product, 40,000 yuan/tons of selling prices very high (〉 more), China leather-making enterprises is difficult to accept employing.Simultaneously, before using above several tanning agent tannings, crust leather all needs pickling, so the neutral salt content in owse is about 50000～70000mg/L, and is suitable with chroming waste liquor.In addition, the molecule of these tanning agents is all less, group is single, the crust leather negative charge of tanning is strong, absorption rate to the negatively charged ion chemical industry material (retanning agent as organic in routine, dyestuff, fatting agent) that uses in subsequent handling is lower, not only cause the serious waste of these materials, also cause the organic contamination content in waste water to improve, and final resultant leather quality has been compared a certain distance with chrome tanned leather.
Summary of the invention
The objective of the invention is for the deficiencies in the prior art, a kind of salt-free not pickling amphiphilic polymers chrome-free tanning agent is provided.
A kind of salt-free not pickling amphiphilic polymers chrome-free tanning agent provided by the invention, it is characterized in that this tanning agent is first to obtain to contain the Mannich base intermediate of aldehyde radical by Mannich reaction with organic amine and the alkanoic that contains active α-H, then this intermediate original position generate contain the allyl monomer of aldehyde radical after, with diallylacetic acid with contain cationic allyl monomer generation radical polymerization and form.Processing step and condition that it is concrete are as follows:
(1) first 60～140 parts of organic amines, 80～100 parts of formaldehyde solutions (37%) stirring at room are mixed, and to regulate its pH be 6.0～8.0, then add 60～110 parts of alkanoics that contain active α-H, reacted under 35～55 ℃ 2～5 hours, and namely got the Mannich base intermediate of following formula:
R in formula
1=-H ,-CH
3,-CH
2CH
3,-CH
2CH
2CH
3Or-CH (CH
3)
2R
2=-H ,-CH
3,-CH
2CH
3,-CH
2CH
2OH or-CH (CH
3) CH
2OH; R
3=-CH
2CH
3,-CH
2CH
2OH or-CH (CH
3) CH
2OH;
(2) add 300～500 parts of water in above-mentioned Mannich base intermediate, 70～120 parts of diallylacetic acids, 125～165 parts contain cationic allyl monomer, 2～10 parts of chain-transfer agents, after being warming up to 75～90 ℃, drip with 10 times of water-reducible 6～10 parts of initiators, time for adding is 1～2 hour, after dripping 75～90 ℃ of insulation reaction 0.5～1.5 hour, be cooled to below 50 ℃, it is that both sexes, outward appearance are the salt-free chrome-free tanning agent of light yellow not pickling to the brown yellow transparent liquid shape that discharging can obtain charge property.
The umber of above material used is mass parts.
The synthetic route of salt-free not pickling amphiphilic polymers chrome-free tanning agent provided by the invention is as follows:
The preferred following concrete technology step of salt-free not pickling amphiphilic polymers chrome-free tanning agent provided by the invention and condition are prepared from:
(1) first 70～105 parts of organic amines, 80～90 parts of formaldehyde solutions (37%) stirring at room are mixed, and to regulate its pH be 6.5～7.5, then add 60～86 parts of alkanoics that contain active α-H, reacted under 40～50 ℃ 3～4 hours, namely get the Mannich base intermediate of following formula:
R in formula
1=-CH
3,-CH
2CH
3Or-CH
2CH
2CH
3R
2=-H ,-CH
3,-CH
2CH
3Or-CH
2CH
2OH; R
3=-CH
2CH
3, CH
2CH
2OH or-CH (CH
3) CH
2OH;
(2) add 350～450 parts of water in above-mentioned Mannich base intermediate, 80～110 parts of diallylacetic acids, 125～150 parts contain cationic allyl monomer, 4～8 parts of chain-transfer agents after being warming up to 80～90 ℃, drip with 10 times of water-reducible 7～9 parts of initiators, time for adding is 1～1.5 hour, 80～90 ℃ of insulation reaction 1～1.5 hour, be cooled to below 50 ℃ after dripping, discharging gets final product.
The umber of above material used is mass parts.
In above-mentioned tanning agent preparation, organic amine used is any in diethylamine, thanomin, monomethyl-ethanolamine, diethanolamine, α-amino isopropyl alcohol or diisopropanolamine (DIPA), preferred diethylamine, monomethyl-ethanolamine diethanolamine and α-amino isopropyl alcohol.
In above-mentioned tanning agent preparation, the alkanoic that contains active α-H used is any in acetaldehyde, propionic aldehyde, butyraldehyde-n, valeraldehyde or isovaleric aldehyde, preferred propionic aldehyde, butyraldehyde-n and valeraldehyde.
In above-mentioned tanning agent preparation, diallylacetic acid used is any in vinylformic acid, methacrylic acid or methylene-succinic acid, preferred vinylformic acid and methacrylic acid; It is used that to contain cationic allyl monomer be any in dimethyl diallyl ammonium chloride or diethyl diallyl ammonium chloride; Initiator used is any in ammonium persulphate, Sodium Persulfate or Potassium Persulphate, preferred Sodium Persulfate and Potassium Persulphate; Chain-transfer agent used is any in n-dodecyl mercaptan, mercaptoethanol or Thiovanic acid, preferred n-dodecyl mercaptan.
The present invention compared with prior art has following advantage:
1, because salt-free not pickling amphiphilic polymers chrome-free tanning agent provided by the invention is cleverly Mannich reaction and Raolical polymerizable to be coupled, and the allyl group intermediate that original position is produced with aldehyde radical participates in the prepared Polymer Tanning Agent that contains aldehyde radical of polyreaction, thereby not only obtained a kind of new chrome-free tanning agent, and avoided the propenal of direct employing strong and stimulating or pollution that the Methylacrylaldehyde monomer brings, produced hard problem.
2, because salt-free not pickling amphiphilic polymers chrome-free tanning agent provided by the present invention is take alkanoic and allyl monomer as main raw material, Mannich reaction and Raolical polymerizable are coupled, original position produces after the allyl monomer contain aldehyde radical directly and the allyl monomer polymerization that contains carboxyl, ammonium, prepare the salt-free chrome-free tanning agent of the not pickling with multiple functional group, thereby its raw material sources are extensive, cheap, production method is simple, workable, production cost is low, has very strong market competition advantage.
3, not only molecular weight is larger due to salt-free not pickling amphiphilic polymers chrome-free tanning agent provided by the present invention, has certain filling properties, and because containing aldehyde radical, has again good flexibility, the pH that produces the tanning effect is 7-8, before making it tanning, crust leather does not need pickling, thereby the tanning performance of this tanning agent can match in excellence or beauty with existing aldehydes tanning agent, can eliminate again because pickling brings the salt that subsequent handling produces and pollute, contained carboxyl and amino, also can promote the skin base to the absorption of follow-up ornamenting material, improve the total quality of leather.
4, with salt-free not pickling amphiphilic polymers chrome-free tanning agent tan leather provided by the invention, just can directly carry out tanning to softening skin because need not pickling, thereby both reduce operation, save the consumption of hydrochlorate, reduced cost, the chromium and the NaCl that have also eliminated traditional tannery from the source pollute.
5, can make the shrinkage temperature of skin base (wet-white leather) reach 83-88 ℃ with salt-free not pickling amphiphilic polymers chrome-free tanning agent provided by the invention tanning, its over-all properties obviously not only is better than the tanning effect of existing organic chrome-free tanning agent both at home and abroad, and tanned crust leather also is convenient to the following process such as split, shaving, also can carry out retanning with organic tanning agent, produce the Chrome-free leather, also can carry out retanning with a small amount of chrome tanning agent, produce semi-chrome tanning (also can significantly reduce consumption and the quantity discharged of chromium).
6, because salt-free not pickling amphiphilic polymers chrome-free tanning agent provided by the invention contains the multiple functional groups such as aldehyde radical, carboxyl and ammonium, therefore tanned crust leather is high to the clean absorption rate of the materials such as retanning agent, fatting agent, dyestuff, can alleviate the discharging leather-making waste water to the pollution of environment.
Embodiment
Below by embodiment, the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further illustrated; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
What deserves to be explained is 1) following examples formaldehyde used is mass percent concentration 37%, and dimethyl diallyl ammonium chloride and diethyl diallyl ammonium chloride are mass percent concentration 65%.2) in following application examples and application Comparative Examples, the shrinkage temperature of skin base is to adopt Hg shrinkage temperature registering instrument to measure.In application Comparative Examples waste liquid, the dyestuff specific absorption is measured according to a kind of like this method: the dyestuff that uses in technique is configured to certain density standard specimen solution, adopts ultraviolet spectrophotometer to measure its absorption peak, the drawing standard curve; Collect the liquid after the initial and stuffing end of dyeing, dilute respectively and measure absorbancy, calculate dyestuff content in liquid by typical curve, replicate measurement is averaged for 3 times.Dyestuff content in the dyeing original liquid is A
1, the dyestuff content after stuffing finishes in waste liquid is A
2The skin base is to the specific absorption of dyestuff=(A
1-A
2)/A
1* 100%.The specific absorption of using fatting agent in Comparative Examples adopts following method to measure: collect stuffing initially and the liquid after finishing, adopt weighting method that the fatting agent content in waste water is measured, the content B of fatting agent in the stuffing original liquid
1The content that stuffing finishes fatting agent in rear liquid is B
2, the skin base is to the specific absorption of fatting agent=(B
1-B
2)/B
1* 100%; Wherein adopt the method for the fatting agent content in gravimetric determination waste water as follows: the 150mL waste liquid to be moved in a separating funnel, add the 3mL vitriol oil and 20mL sherwood oil, sway 5min, note often opening the piston venting.After standing 10min, separate water layer and petroleum ether layer.And then with the grease in 20mL petroleum ether extraction water layer.So coextraction is 3 times.Discard water sample, after saturated NaCl solution washing sherwood oil 3 times (dehydration), the ether layer is transferred to (further dehydration) in the triangular flask that fills the 10g anhydrous sodium sulphate, use filter paper filtering after 12h.Filtrate collection is in placing in advance half an hour and claim in overweight matrass in moisture eliminator.With petroleum ether anhydrous sodium sulphate and filter paper, washing lotion is incorporated in matrass., boil dry on boiling water bath to the residues milliliter in about 70 ℃ of water-bath steaming petroleum ether, and weighing after dry 40min under 103 ℃.Replicate measurement is averaged for 3 times.
Embodiment 1
First with thanomin 60Kg, formaldehyde 100Kg adds in reactor, then to add vitriol oil conditioned reaction system pH be 6.0～6.5, adds acetaldehyde solution (40%) 110Kg, and reaction is 5 hours under 35～40 ℃, gets the Mannich base intermediate.Add entry 300Kg in intermediate, methylene-succinic acid 70 Kg, dimethyl diallyl ammonium chloride 165Kg, mercaptoethanol 2Kg, after being warming up to 75～80 ℃, the interior dropping in the reactor with 100Kg water dilution ammonium persulfate initiator 10Kg, time for adding is 2 hours, 75～80 ℃ of insulation reaction 0.5 hour, be cooled to 50 ℃ with bottom discharge after dripping, namely get product.
Embodiment 2
First with diethylamine 70Kg, formaldehyde 80Kg adds in reactor, then to add vitriol oil conditioned reaction system pH be 6.5～7.0, adds propionic aldehyde 80Kg, and reaction is 4 hours under 50～55 ℃, gets the Mannich base intermediate.Add entry 350Kg in intermediate, vinylformic acid 80Kg, diethyl diallyl ammonium chloride 145Kg, n-dodecyl mercaptan 4Kg after being warming up to 80～85 ℃, drips with the water-reducible Sodium Persulfate initiator of 90Kg 9Kg in reactor, time for adding is 1 hour, 80～85 ℃ of insulation reaction 1 hour, be cooled to 50 ℃ with bottom discharge after dripping, namely get product.
Embodiment 3
First with monomethyl-ethanolamine 75Kg, formaldehyde 80Kg adds in reactor, then to add vitriol oil conditioned reaction system pH be 6.5～7.0, adds propionic aldehyde 60Kg, and reaction is 3.5 hours under 40～45 ℃, gets the Mannich base intermediate.Add entry 400Kg in intermediate, vinylformic acid 90Kg, dimethyl diallyl ammonium chloride 125Kg, n-dodecyl mercaptan 6Kg after being warming up to 85～90 ℃, drips with the water-reducible Potassium Persulphate initiator of 80Kg 8Kg in reactor, time for adding is 1.5 hours, 80～85 ℃ of insulation reaction 1.5 hours, be cooled to 50 ℃ with bottom discharge after dripping, namely get product.
Embodiment 4
First with diethanolamine 105Kg, formaldehyde 90Kg adds in reactor, then to add vitriol oil conditioned reaction system pH be 7.0～7.5, adds valeraldehyde 86Kg, and reaction is 3 hours under 40～45 ℃, gets the Mannich base intermediate.Add entry 450Kg in intermediate, methacrylic acid 110Kg, dimethyl diallyl ammonium chloride 150Kg, n-dodecyl mercaptan 8Kg after being warming up to 85～90 ℃, drips with the water-reducible Sodium Persulfate initiator of 70Kg 7Kg in reactor, time for adding is 1.3 hours, 85～90 ℃ of insulation reaction 1.2 hours, be cooled to 50 ℃ with bottom discharge after dripping, namely get product.
Embodiment 5
With α-amino isopropyl alcohol 90Kg, formaldehyde 85Kg adds in reactor, then to add vitriol oil conditioned reaction system pH be 6.5～7.0, adds butyraldehyde-n 72Kg, and reaction is 4 hours under 45～50 ℃, gets the Mannich base intermediate.Add entry 400 Kg in intermediate, methacrylic acid 100 Kg, diethyl diallyl ammonium chloride 135Kg, n-dodecyl mercaptan 6Kg.After being warming up to 85～90 ℃, drip in the reactor with the water-reducible Potassium Persulphate initiator of 70Kg 7Kg, time for adding is 1.5 hours, 85～90 ℃ of insulation reaction 1.5 hours, is cooled to 50 ℃ with bottom discharge after dripping, and namely gets product.
Embodiment 6
First with diisopropanolamine (DIPA) 140Kg, formaldehyde 95Kg adds in reactor, then to add vitriol oil conditioned reaction system pH be 7.5～8.0, adds isovaleric aldehyde 90Kg, and reaction is 2 hours under 50～55 ℃, gets the Mannich base intermediate.Add entry 500Kg in intermediate, methylene-succinic acid 120Kg, dimethyl diallyl ammonium chloride 160Kg, Thiovanic acid 10Kg after being warming up to 80～85 ℃, drips the water-reducible ammonium persulfate initiator 6Kg with 60Kg in reactor, time for adding is 1 hour, 80～85 ℃ of insulation reaction 0.5 hour, be cooled to 50 ℃ with bottom discharge after dripping, namely get product.
Application examples 1
Should use-case be with salt-free not pickling amphiphilic polymers chrome-free tanning agent tanning ox-hide.
With the ox-hide graywall put into that rotary drum is first washed successively under normal condition, pre-deliming, main deliming, softening, washing, then the salt-free not pickling amphiphilic polymers chrome-free tanning agent 5%, the water 50% that add the present invention to make by the weighing scale of ox-hide graywall, after making it under pH6.0-6.5 normal temperature and rotating 240min, with sodium bicarbonate 0.3%, with 20 times of hot water dilutions, divide and add for three times, every minor tick 20min, turn 120min, pH7.5-8.0 fills into thereafter hot water 150% again, 40 ℃ of temperature, rotate 180min, complete tannery.
The plentiful consolidation of ox-hide wet-white leather of this technique tanning, grain is flat thin, and the shrinkage temperature of mensuration reaches 85 ℃.
Application examples 2
Should use-case be with salt-free not pickling amphiphilic polymers chrome-free tanning agent tanning pigskin.
With the pigskin graywall put into that rotary drum is first washed successively under normal condition, deliming, softening, washing, then the salt-free not pickling amphiphilic polymers chrome-free tanning agent 5%, the water 50% that add the present invention to make by the weighing scale of pigskin graywall, after making it under pH6.0-6.5 normal temperature and rotating 240min, with sodium bicarbonate 0.3%, with 20 times of hot water dilutions, divide and add for three times, every minor tick 20min, turn 120min, pH7.5-8.0 fills into thereafter hot water 150% again, 40 ℃ of temperature, rotate 180min, complete tannery.
The plentiful consolidation of pigskin wet-white leather of this technique tanning, grain is flat thin, and the shrinkage temperature of mensuration reaches 83 ℃.
Application examples 3
Should use-case be with salt-free not pickling amphiphilic polymers chrome-free tanning agent tanning sheepskin.
With the sheepskin graywall put into that rotary drum is first washed successively under normal condition, deliming, softening, washing, then the salt-free not pickling amphiphilic polymers chrome-free tanning agent 4%, the water 50% that add the present invention to make by the weighing scale of sheepskin graywall, after making it under pH6.8-7.2 normal temperature and rotating 120min, fill into again hot water 150%, 40 ℃ of temperature, rotate 180min, complete tannery.
The plentiful consolidation of sheepskin wet-white leather of this technique tanning, grain is flat thin, and the shrinkage temperature of mensuration reaches 87 ℃.
Directly ox, pig, the softening skin of sheep are carried out tanning with the salt-free not pickling amphiphilic polymers of the present invention chrome-free tanning agent, more traditional process for tanning has saved pickling procedure, thereby has also saved the salt that must add in order to suppress sour skin swelling in the pickling process.
Use Comparative Examples 1
This Comparative Examples is with existing modified glutaraldehyde tanning agent tanning sheepskin.
With the sheepskin graywall put into that rotary drum is first washed successively under normal condition, deliming, softening, washing, pickling, then the weighing scale by the sheepskin graywall adds modified glutaraldehyde tanning agent 4%, after normal temperature rotates 120min, divide and add with 20 times of water-reducible sodium bicarbonate 2% of heat for five times, every minor tick 20min, turn 120min, pH6.0-6.5.Fill into hot water 150%, 40 ℃ of temperature are rotated 180min, complete tannery again.
The shrinkage temperature that the sheepskin wet-white leather of this technique tanning is measured reaches 82 ℃.
Use Comparative Examples 2
This Comparative Examples is that above application examples 3 and the chrome-free tanning skin base that application Comparative Examples 1 obtains are carried out the retanning dyeing and finishing, investigates the skin base to the absorption of retanning dyeing and finishing material, further to contrast.
Be 1.0mm with the first water squeezing shaving of skin base to the skin base thickness of application examples 3 and 1 tanning of application Comparative Examples, then put into rotary drum and carry out the retanning dyeing and finishing by the shaving tare weight with following material, operation and condition.
Washing: water 200%, normal temperature rotates 10min, discharge opeing.
Return wet: water 150%, grease-removing agent 0.3%, 35 ℃ of temperature are rotated 40min.
Washing: water 300%, normal temperature rotates 5min, washes twice.
Retanning: water 100%, fatting agent OSL1%, 40 ℃ of temperature are rotated 15min; Synthetic tanning agent OS5% rotates 30min; Formic acid 0.5% rotates 30min, pH4.5-5.0; Synthetic tanning agent RL5% rotates 60min; Acrylic acid double tanning agent ART-I2%, ART-II3%, protein filling FG5% rotates 45min; Formic acid 0.6% adds at twice, every minor tick 15min, pH4.0-4.2, discharge opeing.
Dyeing: water 100%, black dyes SPR2%, temperature 50 C rotates 60min.
Stuffing: fatting agent OSL5%, sulphonated fat-liquoring agent SS5%, phosphatide fatting agent 4%, temperature 50 C rotates 60min; Formic acid 0.8% divides to add for three times, and every minor tick 15min rotates 30min again after adding, pH3.6-3.8, and discharge opeing is also collected waste liquid and is investigated the skin base to the absorbing state of dyestuff and fatting agent.
Washing: water 200%, normal temperature rotates 5min, goes out drum.
The skin base that records the embodiment 3 salt-free not pickling amphiphilic polymers of gained chrome-free tanning agent tannings reaches respectively 99% and 95% to the specific absorption of dyestuff and fatting agent, and the wet-white leather of using Comparative Examples 1 gained modified glutaraldehyde tanning agent tanning is respectively 82% and 80% to the specific absorption of dyestuff and fatting agent.
Claims (10)
1. salt-free not pickling amphiphilic polymers chrome-free tanning agent, it is characterized in that this tanning agent is first to obtain to contain the Mannich base intermediate of aldehyde radical by Mannich reaction with organic amine and the alkanoic that contains active α-H, then this intermediate original position generate contain the allyl monomer of aldehyde radical after, with diallylacetic acid with contain cationic allyl monomer generation radical polymerization and form.
2. salt-free not pickling amphiphilic polymers chrome-free tanning agent as claimed in claim 1 is characterized in that this tanning agent is to be prepared from by following concrete technology step and condition:
(1) first 60～140 parts of organic amines, 80～100 parts of formaldehyde solution stirring at room are mixed, and to regulate its pH be 6.0～8.0, then add 60～110 parts of alkanoics that contain active α-H, reacted under 35～55 ℃ 2～5 hours, namely get the Mannich base intermediate of following formula:
R in formula
1=-H ,-CH
3,-CH
2CH
3,-CH
2CH
2CH
3Or-CH (CH
3)
2R
2=-H ,-CH
3,-CH
2CH
3,-CH
2CH
2OH or-CH (CH
3) CH
2OH; R
3=-CH
2CH
3,-CH
2CH
2OH or-CH (CH
3) CH
2OH.
(2) add 300～500 parts of water in above-mentioned Mannich base intermediate, 70～120 parts of diallylacetic acids, 125～165 parts contain cationic allyl monomer, and 2～10 parts of chain-transfer agents are after being warming up to 75～90 ℃, drip with 10 times of water-reducible 6～10 parts of initiators, time for adding is 1～2 hour, 75～90 ℃ of insulation reaction 0.5～1.5 hour, is cooled to below 50 ℃ after dripping, discharging gets final product
The umber of above material used is mass parts.
3. salt-free not pickling amphiphilic polymers chrome-free tanning agent as claimed in claim 1 is characterized in that this tanning agent is to be prepared from by following concrete technology step and condition:
(1) first 70～105 parts of organic amines, 80～90 parts of formaldehyde solution stirring at room are mixed, and to regulate its pH be 6.5～7.5, then add 60～86 parts of alkanoics that contain active α-H, reacted under 40～50 ℃ 3～4 hours, namely get the Mannich base intermediate of following formula:
R in formula
1=-CH
3,-CH
2CH
3Or-CH
2CH
2CH
3R
2=-H ,-CH
3,-CH
2CH
3Or-CH
2CH
2OH; R
3=-CH
2CH
3, CH
2CH
2OH or-CH (CH
3) CH
2OH;
(2) add 350～450 parts of water in above-mentioned Mannich base intermediate, 80～110 parts of diallylacetic acids, 125～150 parts contain cationic allyl monomer, and 4～8 parts of chain-transfer agents are after being warming up to 80～90 ℃, drip with 10 times of water-reducible 7～9 parts of initiators, time for adding is 1～1.5 hour, 80～90 ℃ of insulation reaction 1～1.5 hour, is cooled to below 50 ℃ after dripping, discharging gets final product
The umber of above material used is mass parts.
4. as claim 1 or 2 or 3 described salt-free not pickling amphiphilic polymers chrome-free tanning agents, it is characterized in that organic amine used in this tanning agent preparation is any in diethylamine, thanomin, monomethyl-ethanolamine, diethanolamine, α-amino isopropyl alcohol or diisopropanolamine (DIPA).
5. as claim 1 or 2 or 3 described salt-free not pickling amphiphilic polymers chrome-free tanning agents, it is characterized in that the alkanoic that contains active α-H used in this tanning agent preparation is any in acetaldehyde, propionic aldehyde, butyraldehyde-n, valeraldehyde or isovaleric aldehyde.
6. salt-free not pickling amphiphilic polymers chrome-free tanning agent as claimed in claim 4 is characterized in that the alkanoic that contains active α-H used in this tanning agent preparation is any in acetaldehyde, propionic aldehyde, butyraldehyde-n, valeraldehyde or isovaleric aldehyde.
7. as claim 1 or 2 or 3 described salt-free not pickling amphiphilic polymers chrome-free tanning agents, it is characterized in that diallylacetic acid used in this tanning agent preparation is any in vinylformic acid, methacrylic acid or methylene-succinic acid; It is used that to contain cationic allyl monomer be any in dimethyl diallyl ammonium chloride or diethyl diallyl ammonium chloride; Initiator used is any in ammonium persulphate, Sodium Persulfate or Potassium Persulphate; Chain-transfer agent used is any in n-dodecyl mercaptan, mercaptoethanol or Thiovanic acid.
8. salt-free not pickling amphiphilic polymers chrome-free tanning agent as claimed in claim 4 is characterized in that diallylacetic acid used in this tanning agent preparation is any in vinylformic acid, methacrylic acid or methylene-succinic acid; It is used that to contain cationic allyl monomer be any in dimethyl diallyl ammonium chloride or diethyl diallyl ammonium chloride; Initiator used is any in ammonium persulphate, Sodium Persulfate or Potassium Persulphate; Chain-transfer agent used is any in n-dodecyl mercaptan, mercaptoethanol or Thiovanic acid.
9. salt-free not pickling amphiphilic polymers chrome-free tanning agent as claimed in claim 5 is characterized in that diallylacetic acid used in this tanning agent preparation is any in vinylformic acid, methacrylic acid or methylene-succinic acid; It is used that to contain cationic allyl monomer be any in dimethyl diallyl ammonium chloride or diethyl diallyl ammonium chloride; Initiator used is any in ammonium persulphate, Sodium Persulfate or Potassium Persulphate; Chain-transfer agent used is any in n-dodecyl mercaptan, mercaptoethanol or Thiovanic acid.
10. salt-free not pickling amphiphilic polymers chrome-free tanning agent as claimed in claim 6 is characterized in that diallylacetic acid used in this tanning agent preparation is any in vinylformic acid, methacrylic acid or methylene-succinic acid; It is used that to contain cationic allyl monomer be any in dimethyl diallyl ammonium chloride or diethyl diallyl ammonium chloride; Initiator used is any in ammonium persulphate, Sodium Persulfate or Potassium Persulphate; Chain-transfer agent used is any in n-dodecyl mercaptan, mercaptoethanol or Thiovanic acid.
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| CN201310039689.4A CN103146850B (en) | 2013-02-01 | 2013-02-01 | Salt-free pickling-free amphoteric polymer chrome-free tanning agent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789715A (en) * | 2015-04-20 | 2015-07-22 | 嘉兴学院 | Salt-free, pickling-free, short-process and little-chromium tanning method |
| CN109072317A (en) * | 2016-03-16 | 2018-12-21 | 科学与工业研究理事会 | Chrome tanning process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009030567A1 (en) * | 2007-09-03 | 2009-03-12 | Basf Se | Method for the production of aqueous formulations, aqueous formulations, and the use thereof |
| CN101532066A (en) * | 2009-04-03 | 2009-09-16 | 陕西科技大学 | Preparation method for toughening type leather tanning agent |
| CN101649361A (en) * | 2009-08-27 | 2010-02-17 | 陕西科技大学 | Method for preparing tannin modified vinyl class polymer tanning agent |
| CN102296130A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院成都有机化学有限公司 | Preparation method of hydrogen bond compounded chromium-free resin tanning agent containing aldehyde group |
| CN102534060A (en) * | 2011-12-21 | 2012-07-04 | 四川亭江新材料股份有限公司 | Method for preparing re-tanning and fatliquoring agent |
-
2013
- 2013-02-01 CN CN201310039689.4A patent/CN103146850B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009030567A1 (en) * | 2007-09-03 | 2009-03-12 | Basf Se | Method for the production of aqueous formulations, aqueous formulations, and the use thereof |
| CN101532066A (en) * | 2009-04-03 | 2009-09-16 | 陕西科技大学 | Preparation method for toughening type leather tanning agent |
| CN101649361A (en) * | 2009-08-27 | 2010-02-17 | 陕西科技大学 | Method for preparing tannin modified vinyl class polymer tanning agent |
| CN102296130A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院成都有机化学有限公司 | Preparation method of hydrogen bond compounded chromium-free resin tanning agent containing aldehyde group |
| CN102534060A (en) * | 2011-12-21 | 2012-07-04 | 四川亭江新材料股份有限公司 | Method for preparing re-tanning and fatliquoring agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789715A (en) * | 2015-04-20 | 2015-07-22 | 嘉兴学院 | Salt-free, pickling-free, short-process and little-chromium tanning method |
| CN109072317A (en) * | 2016-03-16 | 2018-12-21 | 科学与工业研究理事会 | Chrome tanning process |
| CN109072317B (en) * | 2016-03-16 | 2021-07-02 | 科学与工业研究理事会 | Chrome tanning process |
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| CN103146850B (en) | 2014-06-04 |
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