CN105482126A

CN105482126A - Aldehyde group-terminated hyperbranched polymer leather retanning agent and preparation method thereof

Info

Publication number: CN105482126A
Application number: CN201511013489.7A
Authority: CN
Inventors: 任龙芳; 张健; 王学川; 强涛涛
Original assignee: Shaanxi University of Science and Technology
Current assignee: Shaanxi University of Science and Technology
Priority date: 2015-12-31
Filing date: 2015-12-31
Publication date: 2016-04-13
Anticipated expiration: 2035-12-31
Also published as: CN105482126B

Abstract

The invention relates to an aldehyde group-terminated hyperbranched polymer leather retanning agent and a preparation method thereof. The preparation method comprises the following steps of: (1) mixing a trihydroxy compound with glyoxalic acid in a molar ratio of 1:3 to 1:5, heating to 100 DEG C to form a uniform melt state, introducing nitrogen to the bottom of a reactor to discharge air, simultaneously adding a water entrainer and a catalyst, reacting at 100-140 DEG C for 1-6h, stopping nitrogen introduction, reacting at 140-170 DEG C and vacuum degree of 0.02-0.1Mpa for 1-5h, and purifying with ethanol to prepare a monomer B3; and (2) reacting the monomer B with ethanediamine in a ratio of 1:3 to 1:5 to obtain the aldehyde group-terminated hyperbranched polymer leather retanning agent after the reaction is finished. Under the premise of good retanning property, the retanning agent has the advantages that the free formaldehyde content of the leather is reduced, and the shortcoming that the reaction activity is low, the use amount is large and the effect is not obvious in the prior art are overcome.

Description

A kind of terminal aldehyde hyper branched polymer leather retanning agent and preparation method thereof

Technical field

The present invention relates to chemical field, in particular to a kind of terminal aldehyde hyper branched polymer leather retanning agent and preparation method thereof.

Background technology

In leather processing is produced, retanning is supplementing further tanning, and it plays a very important role for the tool such as pliability, fullness ratio, hydrothermal stability improving leather.Conventional aldehyde tanning agent is glutaraldehyde tanning agent, although its have with pelt fast in conjunction with speed, binding capacity is large, finished leather is water-fastness, sweat proof, the advantage such as alkaline-resisting.But due to aldehyde tanned leather not color inhibition, this greatly limits its range of application.Given this defect is planted, the various method of domestic and international employing attempts carrying out modification to glutaraldehyde, to obtaining functional and Application Areas aldehyde tanning agent widely, but this kind of modified retanning agent also exists following problem: one, formaldehyde content is higher, unfriendly to environment; Two, aldehydes retanning agent mostly is micromolecular compound or line polymer, and the little reactive behavior of functionality is lower, and therefore usage quantity is large and result of use is not obvious.

Summary of the invention

The invention provides a kind of terminal aldehyde hyper branched polymer leather retanning agent and preparation method thereof, to under the prerequisite obtaining good retanning performance, reduce the free formaldehyde content in finished leather, and the reactive behavior overcoming prior art existence is lower, usage quantity large and the shortcoming of DeGrain.

In order to achieve the above object, the invention provides a kind of preparation method of terminal aldehyde hyper branched polymer leather retanning agent, comprise the steps:

Step one, trihydric compounds to be mixed with the mol ratio of oxoethanoic acid by 1:3 ~ 1:5, be warmed up to 100 DEG C, when reaction system reaches homogeneous molten state, lead to nitrogen to reactor bottom air is discharged, add water entrainer and the catalyzer of 1% ~ 5% of reaction-ure mixture simultaneously, react 1 ~ 6h at 100 ~ 140 DEG C after, stop logical nitrogen, under the vacuum tightness of 0.02 ~ 0.1Mpa, 1 ~ 5h is reacted, obtained B after purification being carried out to product with ethanol at 140 ~ 170 DEG C ₃monomer;

Step 2, by this B ₃monomer and quadrol react according to the ratio of 1:3 ~ 1:5, and temperature of reaction is 0 ~ 25 DEG C, and reaction 0.5 ~ 3h, can obtain terminal aldehyde hyper branched polymer leather retanning agent after reaction terminates.

Above-mentioned trihydric compounds is TriMethylolPropane(TMP) or glycerine; Diamine compound is quadrol, phenylenediamine, urea or different fluorine that ketone diamines.

Above-mentioned water entrainer is tetracol phenixin, hexanaphthene etc.; Catalyzer is phosphoric acid, sulfuric acid, tosic acid etc.

A kind of terminal aldehyde hyper branched polymer leather retanning agent obtained according to the method described above.

Compared with prior art, advantage of the present invention is:

1, environmentally friendly: owing to not using formaldehyde and the material containing formaldehyde in the preparation process of raw materials used when preparing this hyperbranched polymer and raw material, formaldehyde content effectively reduces, and reduces than the aldehyde tanning agent of routine;

2, result of use is good: product of the present invention is the hyperbranched polymer of high functionality, because having 3 ~ 9 active aldehyde radicals in its each molecule, be easy to form firmly chemical bond with the active group on leather collagen fiber, the shrinkage temperature of finished leather can be improved 12 DEG C before retanning, make the final shrinkage temperature of finished leather reach 128 DEG C; After retanning, the thickness of finished leather increased by 15% before retanning;

3, consumption is little: aldehydes retanning agent mostly is micromolecular compound or line polymer, and the present invention is the hyperbranched polymer of high functionality, therefore its reactive behavior is high, good enhancement is shown to collegen filament, therefore the consumption of retanning agent significantly can be reduced under the prerequisite ensureing finished leather performance, compared with conventional aldehydes retanning agent, use 3%(in the quality of blue skin) this hyperbranched polymer just can reach satisfied performance.The consumption of conventional organic retanning agent is that 5%(is in the quality of blue skin) left and right.

Accompanying drawing explanation

Fig. 1 is B of the present invention ₃the synthesis schematic diagram of monomer;

Fig. 2 is the synthesis schematic diagram of terminal aldehyde hyper branched polymer leather retanning agent of the present invention.

embodiment:

Below in conjunction with embodiment, the present invention is described in detail,

Embodiment 1:

Step one: see Fig. 1, mixes TriMethylolPropane(TMP) with the mol ratio of oxoethanoic acid by 1:3.5, increases the temperature to 100 DEG C; When after the molten state that system becomes homogeneous, nitrogen is passed into until by emptying for the air of inside reactor to reactor bottom, add the phosphoric acid of 20ml tetracol phenixin and 3% (by reactive material gauge) simultaneously, slowly raise system temperature and continue reaction 5h after 110 DEG C; After reaction terminates, stop passing into nitrogen, and system is vacuumized, under vacuum tightness is 0.1Mpa, continues to raise temperature of reaction system continues reaction 3h to 140 DEG C of insulations, after reaction terminates, with 80%(by crude product quality) ethanol (95%) obtained B after purification by liquid extraction is carried out to product ₃monomer;

Step 2: see Fig. 2, by a certain amount of B ₃monomer adds in reactor, then presses B ₃the mol ratio of monomer and quadrol be 1:4 by soluble in water for a certain amount of quadrol, be more slowly added drop-wise to containing in quantitative reactor, temperature of reaction is 20 DEG C, insulation reaction time 2h.

Embodiment 2:

Step one: first glycerine is mixed with the mol ratio of oxoethanoic acid by 1:4, increase the temperature to 100 DEG C; When after the molten state that system becomes homogeneous, nitrogen is passed into until by emptying for the air of inside reactor to reactor bottom, add the tosic acid of 20ml tetracol phenixin and 3% (by reactive material gauge) simultaneously, slowly raise system temperature and continue reaction 4h after 120 DEG C; After reaction terminates, stop passing into nitrogen, and system is vacuumized, under vacuum tightness is 0.08Mpa, continues to raise temperature of reaction system continues reaction 3.5h to 150 DEG C of insulations.After reaction terminates, with 80%(by crude product quality) ethanol (95%) obtained B after purification by liquid extraction is carried out to product ₃monomer;

Step 2: by a certain amount of B ₃monomer adds in reactor, then presses B ₃the mol ratio of monomer and urea be 1:3.5 by soluble in water for a certain amount of urea, be more slowly added drop-wise to containing in quantitative reactor, temperature of reaction is 15 DEG C, insulation reaction time 1h.

Embodiment 3:

Step one: first TriMethylolPropane(TMP) is mixed with the mol ratio of oxoethanoic acid by 1:4.5, increase the temperature to 100 DEG C; When after the molten state that system becomes homogeneous, nitrogen is passed into until by emptying for the air of inside reactor to reactor bottom, add the sulfuric acid of 20ml tetracol phenixin and 3% (by reactive material gauge) simultaneously, slowly raise system temperature and continue reaction 3h after 130 DEG C; After reaction terminates, stop passing into nitrogen, and system is vacuumized, under vacuum tightness is 0.06Mpa, continues to raise temperature of reaction system continues reaction 4h to 160 DEG C of insulations.After reaction terminates, with 80%(by crude product quality) ethanol (95%) obtained B after purification by liquid extraction is carried out to product ₃monomer;

Step 2: by a certain amount of B ₃monomer adds in reactor, then presses B ₃the mol ratio of your ketone diamines of monomer and different fluorine be 1:4.5 by soluble in water for a certain amount of different fluorine that ketone diamines, be more slowly added drop-wise to containing in quantitative reactor, temperature of reaction is 20 DEG C, insulation reaction time 2.5h.

Embodiment 4:

Step one: first TriMethylolPropane(TMP) is mixed with the mol ratio of oxoethanoic acid by 1:5, increase the temperature to 100 DEG C; When after the molten state that system becomes homogeneous, nitrogen is passed into until by emptying for the air of inside reactor to reactor bottom, add the sulfuric acid of 20ml tetracol phenixin and 3% (by reactive material gauge) simultaneously, slowly raise system temperature and continue reaction 1h after 140 DEG C; After reaction terminates, stop passing into nitrogen, and system is vacuumized, under vacuum tightness is 0.06Mpa, continues to raise temperature of reaction system continues reaction 2h to 170 DEG C of insulations.After reaction terminates, with 80%(by crude product quality) ethanol (95%) obtained B after purification by liquid extraction is carried out to product ₃monomer;

Step 2: by a certain amount of B ₃monomer adds in reactor, then presses B ₃the mol ratio of your ketone diamines of monomer and different fluorine be 1:3.5 by soluble in water for a certain amount of different fluorine that ketone diamines, be more slowly added drop-wise to containing in quantitative reactor, temperature of reaction is 0 DEG C, insulation reaction time 5h.

Claims

1. a preparation method for terminal aldehyde hyper branched leather composite tanning agent, comprises the steps:

Step one, trihydric compounds to be mixed with the mol ratio of oxoethanoic acid by 1:3 ~ 1:5, be warmed up to 100 DEG C, when reaction system reaches homogeneous molten state, lead to nitrogen to reactor bottom air is discharged, add 1% ~ 5% water entrainer by reaction-ure mixture and catalyzer simultaneously, react 1 ~ 6h at 100 ~ 140 DEG C after, stop logical nitrogen, under the vacuum tightness of 0.02 ~ 0.1Mpa, 1 ~ 5h is reacted, obtained B after purification being carried out to product with ethanol at 140 ~ 170 DEG C ₃monomer;

2. the preparation method of a kind of terminal aldehyde hyper branched polymer leather retanning agent as claimed in claim 1, is characterized in that: described trihydric compounds is TriMethylolPropane(TMP) or glycerine; Diamine compound is quadrol, phenylenediamine, urea or different fluorine that ketone diamines.

3. the preparation method of a kind of terminal aldehyde hyper branched polymer leather retanning agent as claimed in claim 1 or 2, is characterized in that: described water entrainer is tetracol phenixin or hexanaphthene; Catalyzer is phosphoric acid, sulfuric acid or tosic acid.

4. the terminal aldehyde hyper branched polymer leather retanning agent that obtains of preparation method as claimed in claim 1.