CN117946347A - Protective agent for drying hardened leather cultural relics and preparation method thereof - Google Patents
Protective agent for drying hardened leather cultural relics and preparation method thereof Download PDFInfo
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- CN117946347A CN117946347A CN202410119000.7A CN202410119000A CN117946347A CN 117946347 A CN117946347 A CN 117946347A CN 202410119000 A CN202410119000 A CN 202410119000A CN 117946347 A CN117946347 A CN 117946347A
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- 239000010985 leather Substances 0.000 title claims abstract description 144
- 239000003223 protective agent Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000001035 drying Methods 0.000 title abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 77
- -1 polysiloxane Polymers 0.000 claims abstract description 63
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 46
- 125000002091 cationic group Chemical group 0.000 claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 31
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000002954 polymerization reaction product Substances 0.000 claims description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 20
- 230000008719 thickening Effects 0.000 abstract description 20
- 239000000835 fiber Substances 0.000 abstract description 16
- 102000008186 Collagen Human genes 0.000 abstract description 12
- 108010035532 Collagen Proteins 0.000 abstract description 12
- 229920001436 collagen Polymers 0.000 abstract description 12
- 230000035515 penetration Effects 0.000 abstract description 12
- 239000012466 permeate Substances 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 20
- 230000008595 infiltration Effects 0.000 description 14
- 238000001764 infiltration Methods 0.000 description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 9
- 229920005573 silicon-containing polymer Polymers 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000002791 soaking Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229920001864 tannin Polymers 0.000 description 4
- 239000001648 tannin Substances 0.000 description 4
- 235000018553 tannin Nutrition 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 210000000051 wattle Anatomy 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention belongs to the technical field of leather protection, and discloses a protective agent for drying and hardening leather cultural relics and a preparation method thereof. The monovinyl end-capped polysiloxane used in the invention does not contain structures such as methoxy, ethoxy and the like, is not easy to hydrolyze to generate byproducts, is polymerized with cationic monomers and acrylic ester monomers to be used as a protective agent, and has small particle size by controlling the components and the dosage of the three, so that the prepared protective agent can be applied to repairing dry and hardened leather cultural relics and realize full penetration. The cationic property of the protective agent promotes leather cultural relics to be highly absorbed; after the protective agent uniformly permeates the bonded collagen fibers, the thickening rate, the fiber dispersion degree and the softness of leather cultural relics are obviously improved; the protective agent can also permeate into the fibril level and wrap the fibrils, so that the overall hydrophobicity of the leather cultural relics is improved, and the storage of the dry and hardened leather cultural relics is facilitated.
Description
Technical Field
The invention relates to the technical field of leather cultural relic protection, in particular to a protective agent for drying and hardening leather cultural relics and a preparation method thereof.
Background
Under the influence of the buried environment and the unearthed environment (light, heat, humidity, microorganisms and the like), the collagen of the leather cultural relics is easy to denature and degrade, and the components such as tannins, grease, moisture and the like in the leather are lost, so that the leather cultural relics are aged. The aged leather cultural relics unearthed in the dry area are seriously bonded with collagen fibers, and have the defects of embrittlement, plate hardness, easiness in cracking and the like, thus being dry and hardened leather cultural relics.
The existing protection method for the dry and hardened leather cultural relics uses anionic materials such as anionic softening agents, anionic fatliquoring agents and the like to treat so as to achieve a certain repairing effect. In fact, leather relics are prepared by traditional tanning methods such as vegetable tanning, oil tanning, fumigated tanning, etc. These traditional tanning methods are essentially metal-free organic tanning methods, and the anionic materials cannot be well combined with the organic tanning, so that effective restoration of leather cultural relics cannot be realized. And the leather cultural relics are required to be stored for a long time after being repaired, and how to prevent external moisture from affecting the quality of the leather cultural relics in the storage process is also a key problem. The dry and hardened leather relic fiber is extremely serious in bonding and small in pore, and the existing repairing material cannot fully permeate into the leather relic and cannot effectively repair the leather relic.
In view of this, the present invention has been made.
Disclosure of Invention
In order to solve the problems, the invention provides a protective agent for drying hardened leather cultural relics and a preparation method thereof.
In order to achieve the above object, the first technical scheme adopted by the present invention is as follows:
The protective agent for the dry hardened leather cultural relics is prepared by mixing at least the following components in percentage by mass:
40-70% of cationic monomer, 10-20% of acrylic monomer and 20-40% of monovinyl end-capped polysiloxane;
Wherein the cationic monomer is a cationic acrylate monomer containing a primary amine, secondary amine or tertiary amine structure;
the carbon number of the carbon chain of the acrylic ester monomer is 12 or less;
the monovinyl terminated polysiloxane has the structural formula,
In the structural formula, c=5-30.
Preferably, the cationic acrylate monomer comprises any one or more of ethyl 2- (dimethylamino) acrylate, ethyl 2- (dimethylamino) methacrylate, ethyl 2- (diethylamino) acrylate, ethyl 2- (diethylamino) methacrylate and amino (meth) acrylate.
Preferably, the acrylic monomer comprises any one or more of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate and dodecyl (meth) acrylate.
The second technical scheme adopted by the invention is as follows:
the preparation method of the protective agent for drying the hardened leather cultural relics comprises the following steps:
Uniformly mixing a cationic monomer, an acrylic monomer and first weight of monovinyl terminated polysiloxane to obtain a monomer mixture;
Mixing the monomer mixture with the rest weight of monovinyl terminated polysiloxane, and then carrying out polymerization reaction under the action of an initiator;
wherein the first weight is 40% -80% of the total weight of the monovinyl terminated polysiloxane.
Preferably, the initiator is azo initiator or organic peroxy initiator.
Preferably, the mass of the initiator is 2% -8% of the total mass of the cationic monomer, the acrylic ester monomer and the monovinyl end-capped polysiloxane.
Preferably, the polymerization reaction is carried out at 100-180 ℃ for 10-18 hours.
Preferably, after the polymerization reaction, a small molecular organic acid is used for adjusting the pH of a polymerization reaction product to 2.0-4.0.
Compared with the prior art, the invention has the following beneficial effects:
The monovinyl end-capped polysiloxane used in the invention does not contain structures such as methoxy, ethoxy and the like, is not easy to hydrolyze to generate byproducts, is polymerized with cationic monomers and acrylic ester monomers to be used as a protective agent, and has small particle size by controlling the components and the dosage of the three, so that the prepared protective agent can be applied to repairing dry and hardened leather cultural relics and realize full penetration. The cationic property of the protective agent promotes the leather cultural relics to absorb the leather cultural relics, and the thickening rate, the fiber dispersion degree and the softness of the leather cultural relics are obviously improved after the protective agent is uniformly permeated in the bonded collagen fibers; the protective agent can also permeate into the fibril level of the leather cultural relics and wrap the fibrils, so that the overall hydrophobicity of the leather cultural relics is improved, and the storage of the dry and hardened leather cultural relics is facilitated.
Drawings
FIG. 1 is a scanning electron microscope image of a leather cultural relic simulant before and after the restoration of the protective agent of example 1;
fig. 2 is a graph showing the Si element distribution in the longitudinal section of a leather cultural relic simulant repaired by the protectant of example 1.
Detailed Description
The present invention will be further described in detail with reference to the following embodiments, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The first embodiment of the invention provides a protective agent for drying hardened leather cultural relics, which is prepared by mixing at least the following components in percentage by mass:
40-70% of cationic monomer, 10-20% of acrylic monomer and 20-40% of monovinyl end-capped polysiloxane;
Wherein the cationic monomer is a cationic acrylate monomer containing a primary amine, secondary amine or tertiary amine structure;
the carbon number of the carbon chain of the acrylic ester monomer is 12 or less;
the monovinyl terminated polysiloxane has the structural formula,
In the structural formula, c=5-30.
In the embodiment of the invention, the chain length of the monovinyl end-capped polysiloxane is 5-30, the final reaction product of the monovinyl end-capped polysiloxane within the chain length range cannot be layered in water, and the prepared protective agent has good hydrophobicity; the monovinyl terminated polysiloxane does not contain structures such as methoxy, ethoxy and the like, and is not easy to hydrolyze to generate byproducts.
According to the embodiment of the invention, the particle size of the protective agent is obviously reduced to 5-20 nm by controlling the dosage relation of the cationic monomer, the acrylic ester monomer and the monovinyl end-capped polysiloxane, so that the protective agent can fully and uniformly permeate in the collagen fibers bonded by leather cultural relics.
The protective agent provided by the embodiment of the invention contains a proper amount of cationic groups, can be effectively combined with organic tanning leather with low isoelectric points, is used as a fatliquoring agent for lubricating collagen fibers of leather cultural relics, increases the relative sliding movement of the fibers, and realizes the softening protection of dry hardened leather cultural relics; the cationic group is electrostatically combined with the carboxyl of the collagen side chain, so that the absorptivity of leather cultural relics to the protective agent is obviously improved.
The tannin in the leather cultural relics is lost, the stability is reduced, and diseases are easily generated under the influence of external environment factors; and the leather cultural relics are seriously dehydrated, dried, hardened and flat and collapsed. The protective agent provided by the embodiment of the invention has the performance of a retanning agent, uniformly permeates the grain surface layer, the middle layer and the meat surface layer of the leather cultural relics, is fully combined with collagen molecules, strengthens the structure of the collagen fibers of the leather cultural relics, improves the stability of the collagen fibers and prevents diseases; meanwhile, the protective agent can fully permeate into gaps of collagen fibers and fill the gaps, so that leather cultural relics are endowed with a certain thickening rate, and the repairing effect is further improved.
The leather cultural relics are greatly lost in moisture, the moisture content of the leather cultural relics is greatly different from that of the external environment, and the leather cultural relics are easily influenced by the moisture in the external environment in the preservation process after repair, so that the quality of the leather cultural relics is influenced. The protective agent disclosed by the embodiment of the invention has hydrophobicity, penetrates into the fibril level of leather, realizes the hydrophobic treatment of collagen fibers in leather cultural relics, greatly improves the overall hydrophobicity of the leather of the cultural relics, can not only retain the moisture in the leather cultural relics, but also can separate the external moisture in the preservation process of the leather cultural relics.
The cationic monomer, the acrylic ester monomer and the monovinyl terminated polysiloxane are monomers for preparing the protective agent, and the prepared protective agent is a cationic amphiphilic silicon-containing polymer protective agent.
In some preferred embodiments, the cationic acrylate monomer comprises any one or more of ethyl 2- (dimethylamino) acrylate, ethyl 2- (dimethylamino) methacrylate, ethyl 2- (diethylamino) acrylate, ethyl 2- (diethylamino) methacrylate, amino (meth) acrylate.
In some preferred embodiments, the acrylic monomer comprises any one or more of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and dodecyl (meth) acrylate.
It will be appreciated that the expression "methyl" in brackets of the acrylic monomer means that the monomer may or may not contain methyl groups, for example, methyl (meth) acrylate means that the monomer may be methyl acrylate or methyl methacrylate.
The second embodiment of the invention provides a preparation method of a protective agent for drying hardened leather cultural relics, which comprises the following steps:
Uniformly mixing a cationic monomer, an acrylic monomer and first weight of monovinyl terminated polysiloxane to obtain a monomer mixture;
Mixing the monomer mixture with the rest weight of monovinyl terminated polysiloxane, and then carrying out polymerization reaction under the action of an initiator;
wherein the first weight is 40% -80% of the total weight of the monovinyl terminated polysiloxane.
The temperature and time of the polymerization reaction are not particularly limited, and may be adaptively adjusted by those skilled in the art according to the reaction raw materials and the reaction products. For example, the polymerization reaction may be carried out at 100 to 180℃for 10 to 18 hours.
The initiator is not particularly limited, and one skilled in the art may suitably select and use the initiator according to the components of the polymerization reaction. In some preferred embodiments, the initiator is an azo-type initiator or an organic peroxy-type initiator.
In some preferred embodiments, the mass of the initiator is 2% -8% of the total mass of the monomers.
In some preferred embodiments, in order to further reduce the particle size of the protecting agent, a small molecular organic acid may be used to adjust the pH of the polymerization reaction product to 2.0 to 4.0 after the polymerization reaction, the lower the pH, the smaller the aggregate size, the more advantageous the penetration, but at the same time the hydrophobicity of the polymer is reduced, and both the obtained aggregate size and hydrophobicity are ensured by controlling the pH to 2.0 to 4.0.
In order to make the technical scheme of the invention clearer, the protective agent and the performance for drying the hardened leather cultural relics are described in detail through a plurality of specific embodiments.
In the following examples and comparative examples, "parts" are "parts by weight" and the following measurement methods were used:
method for measuring conversion of monomers
The content (w%) of residual monomer in the polymer was determined according to FZ/T10017-2011 "polyacrylic acid sizing test method for textile sizing residual monomer content determination", and then the conversion of monomer (100% -w%) was calculated.
Particle size measuring method of (II) protective agent
A protectant solution was prepared at a concentration of 1 g/L and was tested using a multi-angle particle size and high sensitivity Zeta potential analyzer (NanoBrook Omni, brookhaven) at a test angle of 90 o for a test time of 3 min and a temperature of 25 ℃.
(III) a preparation method of the dry hardened leather cultural relic simulant: and (5) placing the vegetable tanned leather in a baking oven at 150 ℃ for aging for 8 days to obtain the leather cultural relic simulant. The vegetable tanning (wattle tannin extract tanning) is obtained by tanning acid-soaked cowhide with wattle tannin extract, and the tanning process is shown in table 1.
Table 1 tanning process of vegetable tannage
。
Application method of protective agent in leather cultural relics simulant
The protective agent prepared by the invention is dispersed in warm water at 50 ℃ to prepare protective agent solution with the mass concentration of 3 percent for later use. Firstly, placing the leather cultural relics in 300% (based on the mass of the leather cultural relics, the same applies below) deionized water, soaking for 10h, taking out, then placing in 300% protective agent solution, slowly stirring for 30 min, and then soaking for 10h to finish the repairing treatment. Then, the repaired leather cultural relics are placed in 300% deionized water, and the leather cultural relics are slowly stirred for 10 min to wash away unbound protective agent. And finally, taking out the leather cultural relic simulant and airing.
Test method of absorptivity
The total organic carbon content of the protectant solution before and after soaking of the leather cultural relics simulant was analyzed using a Vario TOC total organic carbon analyzer. Before soaking, the total organic carbon content of the protective agent is recorded as TOC 1; after soaking, the total organic carbon content of the protective agent is recorded as TOC 2; the absorption rate was calculated as follows.
。
Method for testing penetration uniformity of protective agent in leather cultural relics simulant
And (3) performing morphology observation on the longitudinal section of the leather cultural relic simulant subjected to metal spraying by using a scanning electron microscope with the accelerating voltage of 15 kV, and determining the distribution condition of the silicon element of the longitudinal section of the crust leather by using an equipped X-ray energy spectrum. The silicon element distribution was measured as uniform penetration.
Method for testing thickness
The thickness of the leather cultural relics is measured by a leather thickness gauge before and after the restoration, the thickness before the restoration is recorded as thickness 1, the thickness after the restoration is recorded as thickness 2, and the thickening rate is calculated according to the following formula.
。
Method for testing softness
The softness of the leather cultural relics is measured before and after the restoration by using a leather softness tester, the softness before the restoration is recorded as softness 1, the softness after the restoration is recorded as softness 2, and the softness increase rate is calculated according to the following formula.
。
Test method for hydrophobicity
And judging the hydrophobicity of the leather cultural relic simulant according to the water drop infiltration time. The time from contact to complete penetration of a 5.0. Mu.L drop of water from grain side to leather was measured with a contact angle tester at 25 ℃. The water drop infiltration time of the unrepaired leather cultural relics is 7 s.
Example 1
In parts by weight, 12 parts of a monovinyl-terminated polysiloxane (c=20) was added to a four-necked flask, a mixture of 18 parts of the monovinyl-terminated polysiloxane and 55 parts of ethyl 2- (diethylamino) methacrylate and 15 parts of dodecyl methacrylate and 5 parts of dibenzoyl peroxide were added dropwise to the four-necked flask until the temperature was raised to 120 ℃, and then the dropwise addition of 8h parts of dibenzoyl peroxide was completed, followed by thermal insulation reaction 6 h. And regulating the pH value of the product to 3.0 by using formic acid, cooling to room temperature to obtain the protective agent for drying the hardened leather cultural relics, wherein the monomer conversion rate is more than 99%, and the average particle size is 8.1 nm. The absorptivity of the leather cultural relics simulant is 95%. The thickening rate of the repaired leather cultural relics is 20%, the softness increasing rate is 38%, and the water drop infiltration time is 122 min. The scanning electron microscope images of unrepaired leather cultural relics and repaired leather cultural relics are shown in figure 1, and the fiber dispersion degree after repair is remarkably improved. The distribution of Si element in the longitudinal section of the leather cultural relic simulant is shown in figure 2, and the penetration is uniform. The results are shown in Table 2.
TABLE 2 Experimental results for example 1, comparative examples 1-8
。
Comparative example 1
The only difference compared to example 1 is that the monovinyl-terminated siloxane (c=20) is replaced by a monovinyl-terminated siloxane (c=35), and the remaining parameters and the method are the same as in example 1, resulting in a protective agent with a monomer conversion of 76%. The leather cultural relics are unstable after being dispersed in water, and have layering phenomenon, so that the particle size cannot be tested and the leather cultural relics cannot be applied to repairing leather cultural relics. The results are shown in Table 2.
In the comparative example, the added monovinyl terminated polysiloxane chain is too long, so that the chain has large steric hindrance, and cannot be completely polymerized with other monomers, so that the conversion rate is low, and the product is a mixture after the reaction is finished, and has layering phenomenon, so that the application is impossible.
Comparative example 2
The only difference compared to example 1 is that the monovinyl-terminated siloxane (c=20) is replaced by a monovinyl-terminated siloxane (c=4), and the remaining parameters and methods are the same as in example 1, resulting in a protectant with a monomer conversion of greater than 99%. The average grain diameter is 10.2 nm, the thickening rate of the repaired leather cultural relics is 8%, the softness increasing rate is 5%, and the water drop infiltration time is 1.2 min. The results are shown in Table 2.
In this comparative example, the thickening efficiency, softness and hydrophobicity of leather cultural relics mimics are poor due to the too short monovinyl terminated polysiloxane chain added.
Comparative example 3
The only difference compared to example 1 is that dodecyl methacrylate is replaced by hexadecyl methacrylate, and the remaining parameters and the method are the same as in example 1, resulting in a protective agent with a monomer conversion of more than 99%. Cannot be uniformly dispersed in water, precipitation occurs, particle size cannot be tested, and the method cannot be applied to repairing leather cultural relics. The results are shown in Table 2.
In this comparative example, since the added acrylate monomer chain is too long, the polymer aggregate size is large, and it cannot be uniformly dispersed in water, and a macroscopic precipitate is generated, and it cannot be applied.
Comparative example 4
The difference compared with example 1 is that the amount of dodecyl methacrylate is adjusted to 8 parts, and the other parameters and the method are the same as those of example 1, so that a protective agent is obtained, and the monomer conversion is more than 99%. The average grain diameter is 7.3 nm, the absorptivity of the leather cultural relics is 92%, and the leather cultural relics uniformly penetrate into the leather cultural relics. The thickening rate of the repaired leather cultural relics is 2%, the softness increasing rate is 22%, and the water drop infiltration time is 90.4 min. The results are shown in Table 2.
In this comparative example, the polymer filling property was poor because the acrylate monomer was used in too small an amount.
Comparative example 5
The only difference compared to example 1 is that no monovinyl-terminated polysiloxane was added, and the remaining parameters and process are the same as in example 1, yielding a protectant with a monomer conversion of greater than 99%. The average grain diameter is 50.6 nm, the absorptivity of the leather cultural relic simulant is 86%, and the leather cultural relic simulant is uneven in penetration. The thickening rate of the repaired leather cultural relics is 4%, the softness increasing rate is 2%, and the water drop infiltration time is 1.7 min. The results are shown in Table 2.
In the comparative example, the polymer chain has small curling degree and larger particle diameter in water, can not uniformly penetrate in leather cultural relics with serious fiber bonding, and only surface bonding is generated, so that the thickening rate is poor; and the product does not contain monovinyl terminated siloxane, the polymer is poor in hydrophobicity and poor in lubricity on fibers, so that the repaired leather cultural relics are poor in hydrophobicity and low in softness.
Comparative example 6
The only difference compared to example 1 is that the amount of monovinyl-terminated polysiloxane (c=20) was adjusted to 10 parts. 4 parts of monovinyl-terminated polysiloxane (c=20) is added into a four-neck flask, 6 parts of monovinyl-terminated polysiloxane and other monomers are added dropwise together after the temperature is raised to 120 ℃, and the other parameters and the method are the same as those of the example 1, so that the protective agent is obtained, and the monomer conversion rate is more than 99%. The average grain diameter is 37.2 nm, the absorptivity of the leather cultural relic simulant is 90%, and the leather cultural relic simulant is uneven in penetration. The thickening rate of the repaired leather cultural relics is 7%, the softness increasing rate is 6%, and the water drop infiltration time is 6.2 min. The results are shown in Table 2.
In the comparative example, the amount of monovinyl terminated siloxane is small, the polymer chain curl degree is still not large enough, the particle size in water is large, uniform penetration in leather cultural relics can not be realized, and only surface bonding is generated, so that the thickening rate of the repaired leather cultural relics is poor; the polymer has low siloxane chain content and poor penetration, so that the softness is poor; the protective agent with larger particle size cannot penetrate to the fibril level of the bonded leather cultural relics simulant and wrap the fibrils, so that the hydrophobicity is poor.
Comparative example 7
The difference compared with example 1 is that the amount of monovinyl-terminated polysiloxane (c=20) was adjusted to 50 parts, 20 parts of monovinyl-terminated polysiloxane (c=20) was added in a four-necked flask, and after the temperature was raised to 120 ℃,30 parts of monovinyl-terminated polysiloxane were added dropwise together with other monomers in the same manner as in example 1, and the remaining parameters and method were the same, giving a protectant, the monomer conversion was greater than 99%. The average grain diameter is 230.4 nm, the absorptivity of the leather cultural relic simulant is 82%, and the leather cultural relic simulant is uneven in penetration. The thickening rate of the repaired leather cultural relics is 5%, the softness increasing rate is 4%, and the water drop infiltration time is 15.6 min. The results are shown in Table 2.
In the comparative example, the amount of monovinyl terminated polysiloxane (c=20) is too much, and the introduction of a proper amount of monovinyl terminated polysiloxane can increase the curling degree of a long chain of a polymer, so that the polymer protectant is too strong in hydrophobicity and rather increases in particle diameter in water, and cannot uniformly penetrate into leather cultural relics, and only surface bonding occurs, so that the leather cultural relics are poor in thickening rate and softness; and the protective agent with large particle size cannot penetrate to the fibril level of the bonded leather cultural relics simulant and wrap the fibrils, so that the hydrophobicity is poor.
Comparative example 8
Compared with example 1, the method is different only in that the using amount of the 2- (diethylamino) ethyl methacrylate is adjusted to 20 parts, and the other parameters and the method are the same as those of example 1, so that the cationic amphiphilic silicon-containing polymer protective agent is obtained, and the monomer conversion rate is more than 99%. The average grain diameter is 15.8 nm, the absorptivity of the leather cultural relics is 66%, and the leather cultural relics uniformly penetrate into the leather cultural relics. The thickening rate of the repaired leather cultural relics is 4%, the softness increasing rate is 4%, and the water drop infiltration time is 10.6 min. The results are shown in Table 1.
In the comparative example, the leather cultural relics mimics have poor performance because the amount of cationic monomers is too small, the binding sites are small, and the absorptivity of the leather cultural relics mimics is low.
Comparative example 9
The difference from example 1 was that the cationic amphiphilic silicon-containing polymer protectant was obtained by mixing all 30 parts of monovinyl-terminated polysiloxane with other monomers and then dropping the mixture without adding monovinyl-terminated siloxane (c=20) in a four-necked flask in advance, and the other parameters and methods were the same as in example 1, with a monomer conversion of 77%. The leather cultural relics are unstable after being dispersed in water, and have layering phenomenon, so that the particle size cannot be tested and the leather cultural relics cannot be applied to repairing leather cultural relics. The results are shown in Table 1.
In this comparative example, since all of the monovinyl-terminated polysiloxane was mixed with other monomers, it was impossible to polymerize completely by the end of the reaction, and a large amount of monovinyl-terminated polysiloxane remained in the system, resulting in the formation of a mixture of products and delamination phenomenon, which was not applicable.
Example 2
In parts by weight, 4 parts of monovinyl-terminated silicone (c=30) was added to a four-necked flask, a mixture of 16 parts of monovinyl-terminated silicone (c=30) and 70 parts of amino (meth) acrylate and 10 parts of methyl acrylate, and 2 parts of azobisisobutyronitrile were added dropwise to the four-necked flask, dropwise addition of 6h was completed, and then the reaction was incubated for 4 h. And regulating the pH value of the product to 4.0 by using formic acid, and cooling to room temperature to obtain the cationic amphiphilic silicon-containing polymer protective agent, wherein the monomer conversion rate is more than 99%, and the average particle size is 5.2 nm. The absorption rate of the leather cultural relics is 96%, and the leather cultural relics uniformly penetrate into the leather cultural relics. The thickening rate of the repaired leather cultural relics is 16%, the softness increasing rate is 23%, and the water drop infiltration time is 92 min.
Example 3
24 Parts of monovinyl-terminated silicone (c=5) was added to the four-necked flask in parts by weight, a mixture of 16 parts of monovinyl-terminated silicone (c=5) and 40 parts of ethyl 2- (dimethylamino) acrylate and 20 parts of hexyl methacrylate and 8 parts of azobisisobutyronitrile were added dropwise to the four-necked flask until the temperature was raised to 160 ℃, and the dropwise addition of 12h was completed, followed by a heat-retaining reaction of 5 h. And regulating the pH value of the product to 2.0 by using formic acid, and cooling to room temperature to obtain the cationic amphiphilic silicon-containing polymer protective agent, wherein the monomer conversion rate is more than 99%, and the average particle size is 19.7 nm. The absorption rate of the leather cultural relics is 96%, and the leather cultural relics uniformly penetrate into the leather cultural relics. The thickening rate of the repaired leather cultural relics is 24%, the softness increasing rate is 42%, and the water drop infiltration time is 102 min.
Example 4
In parts by weight, 6 parts of monovinyl-terminated silicone (c=15) was added to a four-necked flask, and after the temperature was raised to 130 ℃,14 parts of monovinyl-terminated silicone (c=10), 20 parts of amino (meth) acrylate, 40 parts of a mixture of ethyl 2- (diethylamino) methacrylate, 10 parts of ethyl methacrylate and 10 parts of butyl methacrylate, and 6 parts of diisopropyl peroxydicarbonate were added dropwise to the four-necked flask, and the dropwise addition was completed with 7 h a, followed by thermal insulation reaction 3 h. And regulating the pH value of the product to 3.5 by using formic acid, and cooling to room temperature to obtain the cationic amphiphilic silicon-containing polymer protective agent, wherein the monomer conversion rate is more than 99%, and the average particle size is 7.2 nm. The absorption rate of the leather cultural relics is 94%, and the leather cultural relics uniformly penetrate into the leather cultural relics. The thickening rate of the repaired leather cultural relics is 26%, the softness increasing rate is 39%, and the water drop infiltration time is 94 min.
Example 5
15 Parts of monovinyl-terminated siloxane (c=8) was added to the four-necked flask in parts by weight, and after the temperature was raised to 100 ℃, a mixture of 15 parts of monovinyl-terminated polysiloxane (c=18), 25 parts of ethyl 2- (dimethylamino) acrylate, 25 parts of ethyl 2- (diethylamino) acrylate, 12 parts of butyl acrylate and 8 parts of isobutyl acrylate, and 5 parts of dicyclohexyl peroxydicarbonate were added dropwise to the four-necked flask, and the dropwise addition of 8 h parts was completed, followed by thermal insulation reaction 4 h. And regulating the pH value of the product to 3.8 by using formic acid, and cooling to room temperature to obtain the cationic amphiphilic silicon-containing polymer protective agent, wherein the monomer conversion rate is more than 99%, and the average particle size is 15.3 nm. The absorption rate of the leather cultural relics is 93%, and the leather cultural relics uniformly penetrate into the leather cultural relics. The thickening rate of the repaired leather cultural relics is 24%, the softness increasing rate is 31%, and the water drop infiltration time is 96 min.
Example 6
In parts by weight, 8 parts of monovinyl-terminated siloxane (c=15) was added to a four-necked flask, and after the temperature was raised to 150 ℃, a mixture of 12 parts of monovinyl-terminated polysiloxane (c=7), 65 parts of ethyl 2- (diethylamino) acrylate, 15 parts of octyl acrylate, and 7 parts of dicyclohexyl peroxydicarbonate was added dropwise to the four-necked flask, and the dropwise addition was completed with 8 h parts, followed by a thermal reaction of 4 h. And regulating the pH value of the product to 2.5 by using formic acid, and cooling to room temperature to obtain the cationic amphiphilic silicon-containing polymer protective agent, wherein the monomer conversion rate is more than 99%, and the average particle size is 6.4 nm. The absorption rate of the leather cultural relics is 92%, and the leather cultural relics uniformly penetrate into the leather cultural relics. The thickening rate of the repaired leather cultural relics is 25%, the softness increasing rate is 34%, and the water drop infiltration time is 100 min.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. The protective agent for the dry hardened leather cultural relics is characterized by being prepared by mixing at least the following components in percentage by mass:
40-70% of cationic monomer, 10-20% of acrylic monomer and 20-40% of monovinyl end-capped polysiloxane;
Wherein the cationic monomer is a cationic acrylate monomer containing a primary amine, secondary amine or tertiary amine structure;
the carbon number of the carbon chain of the acrylic ester monomer is 12 or less;
the monovinyl terminated polysiloxane has the structural formula,
In the structural formula, c=5-30.
2. The protective agent for dry hardened leather cultural relics according to claim 1, wherein the cationic acrylate monomer comprises any one or more of ethyl 2- (dimethylamino) acrylate, ethyl 2- (dimethylamino) methacrylate, ethyl 2- (diethylamino) acrylate, ethyl 2- (diethylamino) methacrylate and amino (meth) acrylate.
3. The protective agent for dry hardened leather cultural relics according to claim 1, wherein the acrylic acid ester monomer comprises any one or more of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and dodecyl (meth) acrylate.
4. A method for preparing a protective agent for dry hardened leather relics according to any one of claims 1-3, characterized in that it comprises the following steps:
Uniformly mixing a cationic monomer, an acrylic monomer and first weight of monovinyl terminated polysiloxane to obtain a monomer mixture;
Mixing the monomer mixture with the rest weight of monovinyl terminated polysiloxane, and then carrying out polymerization reaction under the action of an initiator;
wherein the first weight is 40% -80% of the total weight of the monovinyl terminated polysiloxane.
5. The process according to claim 4, wherein the initiator is an azo initiator or an organic peroxy initiator.
6. The preparation method of claim 4, wherein the mass of the initiator is 2% -8% of the total mass of the cationic monomer, the acrylic monomer and the monovinyl-terminated polysiloxane.
7. The method of claim 4, wherein the polymerization is carried out at 100 to 180 ℃ for 10 to 18 hours.
8. The method according to claim 4, wherein the pH of the polymerization reaction product is adjusted to 2.0 to 4.0 using a small-molecule organic acid after the polymerization reaction.
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