CN104498649A - Aldehydic high polymer retanning agent with self-assembly function for free-chrome leather - Google Patents
Aldehydic high polymer retanning agent with self-assembly function for free-chrome leather Download PDFInfo
- Publication number
- CN104498649A CN104498649A CN201510011478.9A CN201510011478A CN104498649A CN 104498649 A CN104498649 A CN 104498649A CN 201510011478 A CN201510011478 A CN 201510011478A CN 104498649 A CN104498649 A CN 104498649A
- Authority
- CN
- China
- Prior art keywords
- aldehyde
- methyl
- retanning
- acrylic resin
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
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 relates to an aldehydic high polymer retanning agent with a self-assembly function for free-chrome leather. The aldehydic high polymer retanning agent is characterized in that the assembly unit of the retanning agent consists of an aldehydic (meth)acrylic resin and tri-block non-ionic amphiphilic polyurethane resin, wherein the aldehydic (meth)acrylic resin is prepared by free radical copolymerization of unsaturated aldehyde and (meth)acrylic acid. According to the hydrogen-bond assembly effect enhanced along with reduction of the pH value between the assembly units, a proper molecular structure is selected, so that the system is assembled and precipitated at the needed pH value and is selectively filled between the skin collagen fibers so as to achieve a retanning-filling effect. Meanwhile, because the retanning agent component has an aldehyde group, the retanning agent can be bound with amino in the skin collagen fibers by covalent bonds and has a certain tanning effect, the hydrothermal stability of the free-chrome leather can be improved to a certain degree, and the free-chrome leather can be endowed with physical and mechanical properties close to those of the chrome tanned leather after retanning as well as good softness, fullness and handfeel.
Description
Technical field
The present invention relates to without chrome tanned leather retanning field, be specifically related to a kind of have self-assembling function without chrome tanned leather with containing the agent of aldehyde high molecular retanning.
Background technology
Retanning has the good reputation of " Golden Touch " in process hides operation.By retanning, tanned leather quality can be promoted further, make finished leather plentiful, soft, and there is better flexibility and elasticity.In traditional tanning industry, macromolecule resin retanning agent is because of its Synthesis and applications technical maturity, and there is the advantages such as active group is many, adjustability of structure is good, and obtain and use widely, it is the maximum Retanning Materials of current consumption, this is wherein general with the use of acrylic resin retanning agent again, is secondly urethane resin retanning agent.
In traditional tanning industry, macromolecule resin retanning agent reaches retanning effect by the negative and positive electric charge ligand complex of the active group on its molecular chain and chromic salts.But along with people's environmental consciousness day by day strengthen and security for all countries, environmental regulation establishment and day by day strengthen, the chromic tanning that traditional process hides adopts more and more is restricted, without chrome tanning technology be just more and more applied in leather production in.The leather produced without chrome tanning technology does not make traditional macromolecule resin retanning agent again can not as before by reaching retanning effect with the ligand complex of chromium containing the reality of chromium.Without in chrome tanned leather retanning, high molecular retanning agent can only act on and just can reach retanning filling effect by producing certain hydrogen bond, hydrophobic bond, Coulomb's force etc. with the protein molecular on collagen, and these non covalent bond effects only just can seem obvious under low ph value (2.0 ~ 3.0) and combine along with pH change is normally reversible.When adopting the process for tanning keeping low ph value, become the dyeing and fat-liquoring that grain effect can be very poor and follow-up to be had a strong impact on, the leather produced like this has no commercial value.Therefore design is a kind of can realize fixing, filling in without chrome tanned leather retanning under reasonable pH value, thus the retanning agent reaching good retanning effect is the active demand of clean leather-making industry.
Chinese patent (CN103255243A) discloses a kind of preparation method of soft type acrylic resin leather composite tanning agent, first method is carry out based on methyl ricinolcic acid and maleic anhydride the maleic mono-ester that esterification generates methyl ricinolcic acid, and obtains methyl ricinolcic acid maleic mono-ester sodium salt monomer with sodium hydroxide neutralization; Then methyl ricinolcic acid maleic mono-ester sodium salt monomer is carried out in water-based system the free-radical polymerized acrylic resin retanning agent obtaining side chain and contain methyl ricinolcic acid structure long chain oleophillic base with vinyl monomer.This invention claims, main chain due to this polymer retanning agent is uniform-distribution with the long linear alkylene side chain of comparatively unfolding, use it for chrome-tanned retanning, softly can remove from office fiber, give the water-repellancy that crust leather is certain, the preparation method of this invention simultaneously eliminates transesterify (or alcoholysis) reaction of Viscotrol C, simplifies production line, reduces production cost.But this retanning agent retanning to as if chrome tanned leather, retanning principle remains and utilizes the carboxyl of acrylic resin and the electric charge coordination of chromic salts negative and positive thus reach retanning filling effect, and without not containing chromium in chrome tanned leather, so lower to the reference value without chrome tanned leather retanning.
Chinese patent (CN103255243A) discloses a kind of preparation method of the hydrogen bond compounded chromium-free resin tanning agent containing aldehyde radical, be by the Nonionic Polyurethane Surfactants containing aldehyde acrylic resin, account for mixture quality 10-30wt% accounting for mixture quality 70-90wt%, obtained by hydrogen bond compound in for the distilled water of mixture quality 1-10 times.This invention claims, due to containing aldehyde radical, and can with the amino in collagen with covalent linkage mortise, when not using other tanning agents, leather can be made to obtain higher hydrothermal stability, and maintain the good select operator of acrylic resin, leather is soft and full.But prepared by this invention is chrome-free tanning agent instead of without chromium retanning agent, major embodiment be that aldehyde radical and amino covalence are cross-linked the tanning effect brought, and packaging assembly is not formed in hydrogen bond compound, what make after tanning is not high enough without chrome tanned leather stability, and therefore reference value is not high.
The present invention with containing aldehyde (methyl) acrylic resin and three block non-ionic type parents urethane resins for assembled unit, based on H-bonding self-assembly construct a kind of containing aldehyde without chrome tanned leather retanning agent, and by the introducing of aldehyde radical, make it have certain tanning effect.In the present invention be (methyl) vinylformic acid and unsaturated aldehyde is Material synthesis containing aldehyde (methyl) acrylic resin, and it is while providing good retanning filling properties, and the existence of aldehyde radical has the effect strengthening tanning effect; Three block non-ionic type parents urethane resins for Material synthesis, have the effect increasing retanning and fill with single end-capped polyoxyethylene ether, polyisocyanates and polyethenoxy ether.This without chrome tanned leather with containing the agent of aldehyde high molecular retanning for the principle without chrome tanned leather retanning is: one, make under appropriate retanning pH value by selecting suitable molecular structure, carboxylate radical on acrylic resin main chain becomes carboxylic acid, and also form the stable step structure be not easily affected by the external environment with the Soxylat A 25-7 block on three block non-ionic type parents urethane resins by hydrogen bond action generation self-assembly, hydrogen bond action between this polymer more and more can replace the hydrogen bond action of polymer and water, H-bonding self-assembly thing is precipitated out and reaches retanning effect, two, in acrylic resin with aldehyde radical, can close with the amino covalence bond in materials with hide glue fibril, there is certain tanning effect, thus give without the good hydrothermal stability of chrome tanned leather and physical mechanics intensity.Can should give on the whole without chrome tanning leather close to the hydrothermal stability after chrome tanned leather retanning, physical and mechanical property and good thickening property of filling etc. containing aldehyde (methyl) acrylic resin, the plentiful softness of finished leather, has good feel.In addition this patent does not add any organic solvent in preparation process, has advantage that is green and environmental protection.
Summary of the invention
In order to accelerate to advance the process of industrialization cleaned without chrome tanning technology, the object of this invention is to provide a kind of preparation method without chrome tanned leather retanning agent built based on H-bonding self-assembly containing aldehyde (methyl) acrylic resin and three block non-ionic type parents urethane resins, system is first obtained containing aldehyde (methyl) acrylic resin and three block non-ionic type parents urethane resins respectively, and then under certain condition, build without chrome tanned leather retanning agent based on H-bonding self-assembly.
The feature without chrome tanned leather retanning agent that one provided by the present invention builds based on H-bonding self-assembly containing aldehyde (methyl) acrylic resin and three block non-ionic type parents urethane resins is:
What 1, the present invention obtained uses containing the agent of aldehyde high molecular retanning without chrome tanned leather, it contains aldehyde (methyl) acrylic resin with aldehyde radical, while good retanning filling properties is provided, aldehyde radical can occur covalently cross-linked with the amino of materials with hide glue fibril, represent certain tanning effect, thus can under the prerequisite of chrome-free tanning agent tanning, give the higher hydrothermal stability of leather and physical mechanics intensity and certain anti-sweat, water resisting property.
2, the present invention utilizes and has two kinds of homopolymer of hydrogen bond action or random copolymers can build self-assembly thought by hydrogen bond to each other, with have hydrogen bond action containing aldehyde (methyl) acrylic resin and three block non-ionic type parents urethane resins for assembled unit, construct a kind of without chrome tanned leather retanning agent.The synthesis technique built without chrome tanned leather retanning agent based on H-bonding self-assembly provided by the present invention does not add any organic solvent, meets the trend of green ecological environmental protection.
What 3, the present invention obtained has certain mutual relationship without chrome tanned leather containing the molecular structure of aldehyde high molecular retanning agent component and the power of hydrogen bond action and retanning system wetting ability, by select appropriate molecular structure containing aldehyde (methyl) acrylic resin and three block non-ionic type parents urethane resins, make to realize assembling, precipitation and certain covalently cross-linked containing aldehyde without chrome tanned leather retanning agent under the retanning pH value needed, thus reach good retanning filling effect.
The present invention is realized by following certain aspects:
One of the present invention is divided into three parts containing aldehyde (methyl) acrylic resin and three block non-ionic type parents urethane resins based on the preparation technology without chrome tanned leather retanning agent that H-bonding self-assembly builds, and namely contains the synthesis of aldehyde (methyl) acrylic resin, the synthesis of three block non-ionic type parents urethane resins and contains the structure of aldehyde H-bonding self-assembly without chrome tanned leather retanning system.
First part is containing the synthesis of aldehyde (methyl) acrylic resin, and wherein the quality proportioning of each component is:
(methyl) vinylformic acid 70-90
Unsaturated aldehyde 10-30
Alkali 5-10
Distilled water 200-600
Water soluble starter 0.1-0.5
Wherein (methyl) acrylic resin is obtained by following special process:
(A) alkali is mixed with distilled water, be mixed with the alkaline solution of 10-30%wt;
(B) in reaction vessel, add distilled water, (methyl) vinylformic acid and unsaturated aldehyde, stir 10-30min;
(C) add water soluble starter, stir 10-30min;
(D) 60-90 DEG C is warmed up to, reaction 2-6h;
(E) cool to 30 DEG C, drip alkali lye adjust ph to 6.0-7.5, obtain containing aldehyde (methyl) acrylic resin;
The synthesis of second section three block non-ionic type parents urethane resin, wherein the quality proportioning of each component is:
Polyisocyanates 1-20
Polyethenoxy ether 20-70
Single end-capped polyoxyethylene ether 30-80
Distilled water 100-500
Catalyzer 0.1-0.3
Three block non-ionic type parents urethane resins are obtained by following special process:
(A) at 120 DEG C, vacuum tightness is respectively to polyethenoxy ether and single end-capped polyoxyethylene ether underpressure distillation 120min under the condition of 0.09MPa, removing moisture;
(B) in the reaction vessel of dry water outlet, add polyethenoxy ether, in stirring, be warmed up to 60-80 DEG C;
(C) in reaction vessel, add catalyzer, stir 10min;
(D) in reaction vessel, drip polyisocyanates, drip in 15-30min, stirring reaction 2h;
(E) in reaction vessel, single end-capped polyoxyethylene ether is added, stirring reaction 2h;
(F) cool to 30 DEG C, under high-speed stirring, add distilled water, three block non-ionic type parents urethane;
Part III containing aldehyde H-bonding self-assembly without the constituent mass proportioning of chrome tanned leather retanning system is:
Containing aldehyde (methyl) acrylic resin 50-80
Three block non-ionic type parents urethane resin 20-50
Obtained by following special process without chrome tanned leather retanning agent containing aldehyde H-bonding self-assembly:
(A) add in reaction vessel containing aldehyde (methyl) acrylic resin, be warming up to 40-60 DEG C, stir 10-30min;
(B) in 30min, be added dropwise to three block non-ionic type parents urethane resins, then at 40-60 DEG C, stir 1h;
(B) be cooled to 30 DEG C namely to obtain containing aldehyde H-bonding self-assembly without chrome tanned leather retanning agent.
Wherein: polyethenoxy ether is number-average molecular weight is 400,1000, the mixture of one or more compositions in 2000; Single end-capped polyoxyethylene ether (Soxylat A 25-7 of methoxy group) for number-average molecular weight be 500,750, mixtures of one or more compositions in 1000; Polyisocyanates is tolylene diisocyanate (TDI), 4,4, the mixture of one or more compositions in-dicyclohexyl methane diisocyanate (HMDI), isophorone diisocyanate (IPDI) or diphenylmethanediisocyanate (MDI); Alkali is the one in sodium hydroxide, potassium hydroxide, salt of wormwood or trolamine; Unsaturated aldehyde is propenal or crotonaldehyde; Water soluble starter is Potassium Persulphate or ammonium persulphate; Described catalyzer is selected from dibutyl tin laurate, stannous octoate.
The invention has the advantages that: by select appropriate molecular structure containing aldehyde (methyl) acrylic resin and three block non-ionic type parents urethane resins, make to penetrate into without after in chrome tanning leather without chrome tanned leather retanning agent, can in Chrome-free environment, the amino on aldehyde radical and materials with hide glue fibril is utilized to produce covalently cross-linked, produce certain tanning effect, give without the leather better properties after chrome tanning; Under the pH value needed, form stable step structure precipitation by H-bonding self-assembly simultaneously, and thus reach well filling retanning effect.In addition, the present invention does not add any organic solvent in the building-up process without chrome tanned leather retanning agent component, meets the trend of environmental protection.
Embodiment:
Embodiment one
1. containing the synthesis of aldehyde (methyl) acrylic resin
140g distilled water, 13.02g Acrylic Acid Monomer and 5.58g propenal is added in the four-necked bottle with agitator, reflux condensing tube.Start agitator, be uniformly mixed 30min; Add 0. 02g ammonium persulphate, after continuing to stir 10min, be warming up to 80 DEG C; In 80 DEG C of reaction 2h, after cooling down to 30 DEG C, with the aqueous sodium hydroxide solution regulation system pH to 6.0 of the l0wt% prepared.Namely obtained solid content be l0wt% containing aldehyde (methyl) acrylic resin.
2. the synthesis of three block non-ionic type parents urethane resins
At 120 DEG C, vacuum tightness is respectively to polyethenoxy ether and single end-capped polyoxyethylene ether underpressure distillation 120min under the condition of 0.09MPa, removing moisture.The molecular weight adding 5.6g in the four-necked bottle with agitator, thermometer is 1000 polyethenoxy ethers, 80 DEG C are heated under stirring, add the dibutyl tin laurate of 0. 0lg, be uniformly mixed 10min, then the tolylene diisocyanate (TDI) of 2.8g is dripped, drip in 15min, stirring reaction 2h.After to add 8.4g molecular weight be 1000 single end-capped polyoxyethylene ethers, continue reaction 2h.Then be cooled to 30 DEG C, add 140g distilled water under high-speed stirring, namely obtained solid content is the three block non-ionic type parents urethane resins of 10 wt %.
3. containing the structure of aldehyde H-bonding self-assembly without chrome tanned leather retanning system
In reaction vessel, add 50g solid content is that l0wt% contains aldehyde (methyl) acrylic resin, be warming up to 40-60 DEG C, in 30min in reaction vessel, be added dropwise to 50g solid content is again l0wt% tri-block non-ionic type parents urethane resins, stir 1h, be cooled to 30 DEG C and namely obtain containing aldehyde H-bonding self-assembly without chrome tanned leather retanning agent.
Embodiment two
1. containing the synthesis of aldehyde (methyl) acrylic resin
140g distilled water, 13.02g Acrylic Acid Monomer and 5.58g propenal is added in the four-necked bottle with agitator, reflux condensing tube.Start agitator, be uniformly mixed 30min; Add 0. 02g ammonium persulphate, after continuing to stir 10min, be warming up to 80 DEG C; In 80 DEG C of reaction 2h, after cooling down to 30 DEG C, with the aqueous sodium hydroxide solution regulation system pH to 6.0 of the l0wt% prepared.Namely obtained solid content be l0wt% containing aldehyde (methyl) acrylic resin.
2. the synthesis of three block non-ionic type parents urethane resins
At 120 DEG C, vacuum tightness is respectively to polyethenoxy ether and single end-capped polyoxyethylene ether underpressure distillation 120min under the condition of 0.09MPa, removing moisture.The molecular weight adding 5.6g in the four-necked bottle with agitator, thermometer is 1000 polyethenoxy ethers, 80 DEG C are heated under stirring, add the dibutyl tin laurate of 0. 0lg, be uniformly mixed 10min, then the tolylene diisocyanate (TDI) of 2.8g is dripped, drip in 15min, stirring reaction 2h.After to add 8.4g molecular weight be 1000 single end-capped polyoxyethylene ethers, continue reaction 2h.Then be cooled to 30 DEG C, add 140g distilled water under high-speed stirring, namely obtained solid content is the three block non-ionic type parents urethane resins of 10 wt %.
3. containing the structure of aldehyde H-bonding self-assembly without chrome tanned leather retanning system
In reaction vessel, add 80g solid content is that l0wt% contains aldehyde (methyl) acrylic resin, be warming up to 40-60 DEG C, in 30min in reaction vessel, be added dropwise to 20g solid content is again l0wt% tri-block non-ionic type parents urethane resins, stir 1h, be cooled to 30 DEG C and namely obtain containing aldehyde H-bonding self-assembly without chrome tanned leather retanning agent.
Embodiment three
1. containing the synthesis of aldehyde (methyl) acrylic resin
140g distilled water, 13.02g Acrylic Acid Monomer and 5.58g propenal is added in the four-necked bottle with agitator, reflux condensing tube.Start agitator, be uniformly mixed 30min; Add 0. 02g ammonium persulphate, after continuing to stir 10min, be warming up to 80 DEG C; In 80 DEG C of reaction 2h, after cooling down to 30 DEG C, with the aqueous sodium hydroxide solution regulation system pH to 6.0 of the l0wt% prepared.Namely obtained solid content be l0wt% containing aldehyde (methyl) acrylic resin.
2. the synthesis of three block non-ionic type parents urethane resins
At 120 DEG C, vacuum tightness is respectively to polyethenoxy ether and single end-capped polyoxyethylene ether underpressure distillation 120min under the condition of 0.09MPa, removing moisture.The molecular weight adding 5.6g in the four-necked bottle with agitator, thermometer is 2000 polyethenoxy ethers, 80 DEG C are heated under stirring, add the dibutyl tin laurate of 0. 0lg, be uniformly mixed 10min, then the isophorone diisocyanate (IPDI) of 2.8g is dripped, drip in 15min, stirring reaction 2h.After to add 8.4g molecular weight be 500 single end-capped polyoxyethylene ethers, continue reaction 2h.Then be cooled to 30 DEG C, add 140g distilled water under high-speed stirring, namely obtained solid content is the three block non-ionic type parents urethane resins of 10 wt %.
3. containing the structure of aldehyde H-bonding self-assembly without chrome tanned leather retanning system
In reaction vessel, add 50g solid content is that l0wt% contains aldehyde (methyl) acrylic resin, be warming up to 40-60 DEG C, in 30min in reaction vessel, be added dropwise to 50g solid content is again l0wt% tri-block non-ionic type parents urethane resins, stir 1h, be cooled to 30 DEG C and namely obtain containing aldehyde H-bonding self-assembly without chrome tanned leather retanning agent.
Embodiment four
1. containing the synthesis of aldehyde (methyl) acrylic resin
140g distilled water, 26.04g Acrylic Acid Monomer and 11.16g propenal is added in the four-necked bottle with agitator, reflux condensing tube.Start agitator, be uniformly mixed 30min; Add 0. 02g ammonium persulphate, after continuing to stir 10min, be warming up to 80 DEG C; In 80 DEG C of reaction 2h, after cooling down to 30 DEG C, with the aqueous sodium hydroxide solution regulation system pH to 6.0 of the 20wt% prepared.Namely obtained solid content be 20wt% containing aldehyde (methyl) acrylic resin.
2. the synthesis of three block non-ionic type parents urethane resins
At 120 DEG C, vacuum tightness is respectively to polyethenoxy ether and single end-capped polyoxyethylene ether underpressure distillation 120min under the condition of 0.09MPa, removing moisture.The molecular weight adding 11.2g in the four-necked bottle with agitator, thermometer is 1000 polyethenoxy ethers, 80 DEG C are heated under stirring, add the dibutyl tin laurate of 0. 0lg, be uniformly mixed 10min, then the isophorone diisocyanate (IPDI) of 5.6g is dripped, drip in 15min, stirring reaction 2h.After to add 16.8g molecular weight be 1000 single end-capped polyoxyethylene ethers, continue reaction 2h.Then be cooled to 30 DEG C, add 140g distilled water under high-speed stirring, namely obtained solid content is the three block non-ionic type parents urethane resins of 20 wt %.
3. containing the structure of aldehyde H-bonding self-assembly without chrome tanned leather retanning system
In reaction vessel, add 50g solid content is that 20wt% contains aldehyde (methyl) acrylic resin, be warming up to 40-60 DEG C, in 30min in reaction vessel, be added dropwise to 50g solid content is again 20wt% tri-block non-ionic type parents urethane resins, stir 1h, be cooled to 30 DEG C and namely obtain containing aldehyde H-bonding self-assembly without chrome tanned leather retanning agent.
Embodiment five
1. containing the synthesis of aldehyde (methyl) acrylic resin
160g distilled water, 13.02g Acrylic Acid Monomer and 5.58g propenal is added in the four-necked bottle with agitator, reflux condensing tube.Start agitator, be uniformly mixed 30min; Add 0. 02g Potassium Persulphate, after continuing to stir 10min, be warming up to 80 DEG C; In 80 DEG C of reaction 2h, after cooling down to 30 DEG C, with the aqueous sodium hydroxide solution regulation system pH to 6.0 of the l0wt% prepared.Namely obtained solid content be l0wt% containing aldehyde (methyl) acrylic resin.
2. the synthesis of three block non-ionic type parents urethane resins
At 120 DEG C, vacuum tightness is respectively to polyethenoxy ether and single end-capped polyoxyethylene ether underpressure distillation 120min under the condition of 0.09MPa, removing moisture.The molecular weight adding 5.6g in the four-necked bottle with agitator, thermometer is 400 polyethenoxy ethers, 80 DEG C are heated under stirring, add the dibutyl tin laurate of 0. 0lg, be uniformly mixed 10min, then the isophorone diisocyanate (IPDI) of 2.8g is dripped, drip in 15min, stirring reaction 2h.After to add 8.4g molecular weight be 1000 single end-capped polyoxyethylene ethers, continue reaction 2h.Then be cooled to 30 DEG C, add 140g distilled water under high-speed stirring, namely obtained solid content is the three block non-ionic type parents urethane resins of 10 wt %.
3. containing the structure of aldehyde H-bonding self-assembly without chrome tanned leather retanning system
In reaction vessel, add 50g solid content is that l0wt% contains aldehyde (methyl) acrylic resin, be warming up to 40-60 DEG C, in 30min in reaction vessel, be added dropwise to 50g solid content is again l0wt% tri-block non-ionic type parents urethane resins, stir 1h, be cooled to 30 DEG C and namely obtain containing aldehyde H-bonding self-assembly without chrome tanned leather retanning agent.
Claims (3)
1. patent of the present invention relate to a kind of have self-assembling function without chrome tanned leather with containing the agent of aldehyde high molecular retanning, be characterised in that assembled unit is containing aldehyde (methyl) acrylic resin and three block non-ionic type parents urethane resins; Obtained by unsaturated aldehyde and (methyl) vinylformic acid radical copolymerization containing aldehyde (methyl) acrylic resin; Three block nonionic parents urethane resins are progressively polymerized obtained by single end-capped polyoxyethylene ether, polyisocyanates and polyethenoxy ether.
2. wherein assembled unit quality to account for the ratio of assembly total mass as follows:
Containing aldehyde (methyl) acrylic resin 50-80%
Three block non-ionic type parents urethane resin 20-50%
Wherein, the constituent mass proportioning of three block non-ionic type parents urethane resins is:
Polyisocyanates 1-20
Polyethenoxy ether 20-70
Single end-capped polyoxyethylene ether 30-80
Distilled water 100-500
Catalyzer 0.1-0.3
Three block non-ionic type parents urethane resins are obtained by following special process:
At 120 DEG C, vacuum tightness is respectively to single end-capped polyoxyethylene ether and polyethenoxy ether underpressure distillation 120min under the condition of 0.09MPa, removing moisture;
In the dry reaction vessel dewatered, add polyethenoxy ether, in stirring, be warmed up to 60-80 DEG C;
In reaction vessel, add catalyzer, stir 10min;
In reaction vessel, drip vulcabond, drip in 15-30min, stirring reaction 2h;
Single end-capped polyoxyethylene ether is added, stirring reaction 2h in reaction vessel;
Cool to 30 DEG C, under high-speed stirring, add distilled water, three block non-ionic type parents urethane;
Quality proportioning containing aldehyde (methyl) acrylic resin component is:
(methyl) vinylformic acid 70-90
Unsaturated aldehyde 10-30
Alkali 5-10
Distilled water 200-600
Water soluble starter 0.1-0.5
Wherein obtained by following special process containing aldehyde (methyl) acrylic resin:
Alkali is mixed with distilled water, is mixed with the alkaline solution of 10-30%wt;
In reaction vessel, add distilled water, (methyl) vinylformic acid and unsaturated aldehyde, stir 10-30min;
Add water soluble starter, stir 10-30min;
Be warmed up to 60-90 DEG C, reaction 2-6h;
Cool to 30 DEG C, drip alkali lye adjust ph to 6.0-7.5, obtain containing aldehyde (methyl) acrylic resin;
Obtained by following special process without chrome tanned leather retanning agent containing aldehyde H-bonding self-assembly:
Add in reaction vessel containing aldehyde (methyl) acrylic resin, be warming up to 40-60 DEG C, stir 10-30min;
In 30min, be added dropwise to three block non-ionic type parents urethane resins, then at 40-60 DEG C, stir 1h;
Be cooled to 30 DEG C namely to obtain containing aldehyde H-bonding self-assembly without chrome tanned leather retanning agent.
3. a kind of preparation method containing the agent of aldehyde high molecular retanning without chrome tanned leather with self-assembling function according to claim 1, is characterized in that: described polyethenoxy ether is number-average molecular weight is 400,1000, mixtures of one or more compositions in 2000; Single end-capped polyoxyethylene ether (Soxylat A 25-7 of methoxy group) for number-average molecular weight be 500,750, mixtures of one or more compositions in 1000; Polyisocyanates is tolylene diisocyanate (TDI), 4,4, the mixture of one or more compositions in-dicyclohexyl methane diisocyanate (HMDI), isophorone diisocyanate (IPDI) or diphenylmethanediisocyanate (MDI); Unsaturated aldehyde is propenal or crotonaldehyde; Alkali is the one in sodium hydroxide, potassium hydroxide, salt of wormwood or trolamine; Water soluble starter is Potassium Persulphate or ammonium persulphate; Described catalyzer is selected from dibutyl tin laurate, stannous octoate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510011478.9A CN104498649A (en) | 2015-01-12 | 2015-01-12 | Aldehydic high polymer retanning agent with self-assembly function for free-chrome leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510011478.9A CN104498649A (en) | 2015-01-12 | 2015-01-12 | Aldehydic high polymer retanning agent with self-assembly function for free-chrome leather |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104498649A true CN104498649A (en) | 2015-04-08 |
Family
ID=52940099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510011478.9A Pending CN104498649A (en) | 2015-01-12 | 2015-01-12 | Aldehydic high polymer retanning agent with self-assembly function for free-chrome leather |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104498649A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384899A (en) * | 2015-12-07 | 2016-03-09 | 四川大学 | Preparation method for Y-type tri-block non-ionic polyurethane Bola surfactant |
| CN111777738A (en) * | 2020-07-28 | 2020-10-16 | 陕西科技大学 | Vegetable oil derivative modified amphoteric polyurethane retanning agent and preparation method thereof |
| CN115807137A (en) * | 2021-09-14 | 2023-03-17 | 四川大学 | Preparation method of hydrogen bond-based chrome-free tanned leather fluorine-containing retanning agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4961750A (en) * | 1987-07-27 | 1990-10-09 | Rohm Gmbh | Acrylate 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 |
-
2015
- 2015-01-12 CN CN201510011478.9A patent/CN104498649A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4961750A (en) * | 1987-07-27 | 1990-10-09 | Rohm Gmbh | Acrylate 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384899A (en) * | 2015-12-07 | 2016-03-09 | 四川大学 | Preparation method for Y-type tri-block non-ionic polyurethane Bola surfactant |
| CN105384899B (en) * | 2015-12-07 | 2017-11-14 | 四川大学 | A kind of preparation method of Y types three block nonionic polyurethane Bola surfactants |
| CN111777738A (en) * | 2020-07-28 | 2020-10-16 | 陕西科技大学 | Vegetable oil derivative modified amphoteric polyurethane retanning agent and preparation method thereof |
| CN111777738B (en) * | 2020-07-28 | 2021-10-15 | 陕西科技大学 | Vegetable oil derivative modified amphoteric polyurethane retanning agent and preparation method thereof |
| CN115807137A (en) * | 2021-09-14 | 2023-03-17 | 四川大学 | Preparation method of hydrogen bond-based chrome-free tanned leather fluorine-containing retanning agent |
| CN115807137B (en) * | 2021-09-14 | 2024-01-26 | 四川大学 | Preparation method of hydrogen bond-based fluorine-containing retanning agent for chrome-free tanning |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107573474B (en) | Silicone-modified waterborne polyurethane-acrylic resin emulsion and preparation method thereof | |
| CN105330813B (en) | A kind of synthetic method of process hides organic silicon modified aqueous polyurethane | |
| CN104292414B (en) | A kind of organic-silicon-modified both sexes aqueous polyurethane emulsion and preparation method thereof | |
| CN104193946B (en) | self-extinction polyurethane resin and preparation method thereof | |
| CN104628982B (en) | A kind of preparation method of alkali lignin base water polyurethane | |
| CN106543877B (en) | The modified polyurethane woodwork coating of water polyacrylic acid containing organosilicon and its preparation method and application | |
| CN109554153A (en) | A kind of preparation method and application of collagen base adhesive | |
| CN101240354B (en) | Acrylic resin/SiO2 nano composite tanning agent and preparation method thereof | |
| CN106543406A (en) | A kind of aqueous pu dispersions slurry and its method for preparing wet method bass | |
| CN102701999B (en) | Cationic water-based polyurethane leather coating agent and preparation method thereof | |
| US20080305349A1 (en) | Energy-curing breathable coatings (combined) | |
| CN104498649A (en) | Aldehydic high polymer retanning agent with self-assembly function for free-chrome leather | |
| CN107722236B (en) | Preparation method and application of organic silicon modified self-extinction waterborne polyurethane for synthetic leather | |
| CN103965715A (en) | Water-based glass coating | |
| CN103804613A (en) | Preparation method of organic silicon modified cationic waterborne antibacterial polyurethane emulsion | |
| CN106149381A (en) | A kind of cation type organic silicon modified waterborne PUA WP with self-crosslinking structure and preparation method thereof | |
| CN106543881A (en) | A kind of water polyacrylic acid modified polyurethane water-repellent paint and its preparation method and application | |
| CN103805122A (en) | Waterborne polyurethane patch adhesive and preparation method thereof | |
| CN105837773A (en) | Preparation method of double-modified hyperbranched waterborne polyurethane emulsion with silicone and renewable vegetable oil | |
| CN101280053B (en) | Method for preparing acrylic-modified waterborneppolyurethane from reproducible polylol | |
| CN101871024B (en) | Method for preparing aldehyde-containing polyurethane-acrylate resin tanning agent | |
| CN102977764A (en) | Weather-resistant leather finishing agent | |
| CN104531916B (en) | A kind of preparation method of the retanning agent without chrome leather built based on H-bonding self-assembly | |
| CN101921362A (en) | Trimethylolpropane diallyl ether modified acrylate micro-gel emulsion and preparation method thereof | |
| CN111004366A (en) | Tissue organ-imitated polyurethane-based composite material for dummy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150408 |
|
| WD01 | Invention patent application deemed withdrawn after publication |