CN116082196B - Carbamide terminated carbamate compound and preparation method and application thereof - Google Patents
Carbamide terminated carbamate compound and preparation method and application thereof Download PDFInfo
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- CN116082196B CN116082196B CN202310047537.2A CN202310047537A CN116082196B CN 116082196 B CN116082196 B CN 116082196B CN 202310047537 A CN202310047537 A CN 202310047537A CN 116082196 B CN116082196 B CN 116082196B
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- -1 carbamate compound Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title description 12
- 235000013877 carbamide Nutrition 0.000 title description 6
- 239000004202 carbamide Substances 0.000 title description 6
- 229920002334 Spandex Polymers 0.000 claims abstract description 61
- 239000004759 spandex Substances 0.000 claims abstract description 61
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 238000004043 dyeing Methods 0.000 claims abstract description 39
- 238000004383 yellowing Methods 0.000 claims abstract description 39
- 238000009987 spinning Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 17
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 13
- 229940126062 Compound A Drugs 0.000 claims description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 7
- 238000000578 dry spinning Methods 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- XHJGXOOOMKCJPP-UHFFFAOYSA-N 2-[tert-butyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(C(C)(C)C)CCO XHJGXOOOMKCJPP-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 4
- 230000004075 alteration Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 45
- 125000001931 aliphatic group Chemical group 0.000 description 20
- 239000000975 dye Substances 0.000 description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 14
- 239000012752 auxiliary agent Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 150000003512 tertiary amines Chemical class 0.000 description 8
- 229920003226 polyurethane urea Polymers 0.000 description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- 239000000980 acid dye Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000008149 soap solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical group CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides an carbamido-terminated carbamate compound, a preparation method and application thereof, wherein the carbamido-terminated carbamate compound has the following structural formula:
Description
Technical Field
The invention relates to the technical field of material organic chemicals, in particular to an carbamido-terminated carbamate compound and a preparation method and application thereof.
Background
Spandex, i.e., polyurethane elastic fiber, is a textile fiber having the best elastic elongation and elastic recovery, and has wide application in textile industry. The molecular structure of the spandex consists of a soft section and a hard section, wherein the aggregation state of the hard section is a fiber supporting framework, the polarity is strong, and dye is difficult to enter; the soft segment has weak polarity, but has poor acting force on dye molecules, so the spandex fiber lacks a dye base, is difficult to color and has low color fastness.
In order to solve the dyeing problem of spandex, in the prior published patent, a chain extender or terminator containing tertiary amine is generally adopted to introduce tertiary amine groups on the molecular chain of the spandex as dyeing bases so as to improve the dyeing property of the spandex. However, the proportion of the chain extender and the terminator on the molecular chain of the spandex is small, the improvement on the dyeing property is limited, in addition, the spandex is easy to yellow at high temperature, color difference is caused, and the dyeing effect is influenced. The existing mode for preventing yellowing is usually to add UDT (bis (N, N-dimethyl hydrazino-4-phenyl) methane) into a spinning solution as an anti-yellowing agent, however, urea groups exist in the UDT, so that the solubility of the UDT in a spandex spinning solution is poor, and the anti-yellowing effect of the UDT is limited. The existing method for improving the dyeing property of the spandex is difficult to solve the dyeing and yellowing problems of the spandex, and the existing technology for improving the dyeing property of the spandex generally changes the molecular structure of the spandex and has a certain influence on the performance of the spandex. Therefore, in order to improve the dyeing effect of spandex, it is necessary to develop a new spandex dyeing auxiliary agent.
Disclosure of Invention
In order to solve the problems, the invention provides an ureido-terminated carbamate compound, a preparation method and application thereof, which improve the dyeing effect of spandex on acid dye without changing the molecular structure of the spandex and can avoid yellowing of the spandex at high temperature. The specific scheme is as follows:
an ureido terminated urethane compound having the structure represented by the formula:
Wherein R 1 is an aliphatic structure having at least 1 carbon;
R 2 and R 3 are aliphatic structures having at least 2 carbons;
R 4 is an aliphatic structure, or an alicyclic structure containing at least one aliphatic ring, or an aromatic structure containing at least one benzene ring;
R 5 and R 6 are aliphatic structures having at least 1 carbon;
n.ltoreq.5, preferably less than 3, preferably 1.
A process for the preparation of an ureido terminated urethane compound comprising the steps of:
step 1): reacting ase:Sub>A compound A with ase:Sub>A compound B according to ase:Sub>A molar ratio of 1:2 to generate an isocyanate-terminated compound i with ase:Sub>A B-A-B structure;
Step 2): reacting the compound C with the compound i according to ase:Sub>A molar ratio of 2:1 to generate an ureido-terminated carbamate compound ii with ase:Sub>A C-B-A-B-C structure, wherein the compound ii is the finally obtained ureido-terminated carbamate compound;
Wherein the structure of the compound A is shown as a formula (1),
In formula (1), R 1 is an aliphatic structure having at least 1 carbon, and R 2 and R 3 are aliphatic structures having at least 2 carbons;
The structure of the compound B is shown as a formula (2),
O=c=n-R 4 -n=c=o formula (2),
In the formula (2), R 4 is an aliphatic structure, or an alicyclic structure containing at least one aliphatic ring, or an aromatic structure containing at least one benzene ring;
the structure of the compound i is shown as a formula (3),
The structure of the compound C is shown as a formula (4),
In formula 4, R 5 and R 6 are aliphatic structures having at least 1 carbon.
Alternatively, the reaction conditions of step 1) are specifically: compound a and compound B were dissolved in a polar solvent at a molar ratio of 1:2 and then reacted at a temperature of 35-50 ℃ for 2h.
Alternatively, the reaction conditions of step 2) are reaction at a temperature of 10-60 ℃ for 0.5h.
Optionally, the compound A is at least one of N-methyldiethanolamine and N-tert-butyldiethanolamine.
Optionally, the compound B is one or more of MDI, TDI, HDI, IPDI.
Optionally, the compound C is unsymmetrical dimethylhydrazine.
The preparation method of the anti-yellowing and easy-to-dye spandex is characterized in that the carbamido-terminated carbamate compound is added into a spandex spinning solution, and the anti-yellowing and easy-to-dye spandex is obtained after dry spinning, wherein the addition amount of the carbamido-terminated carbamate compound is 0.1-5% of the mass of the spandex fiber, and preferably 0.1-2%.
Optionally, the preparation of the spandex spinning solution comprises the following steps:
Step a): mixing a dihydroxy compound with diisocyanate to react to obtain isocyanate terminated prepolymer;
Step b): dissolving the prepolymer obtained in the step a) in a solvent to prepare a prepolymer solution;
step c): after the prepolymer solution is cooled, carrying out chain extension reaction and chain termination reaction to obtain a spandex spinning solution;
the use of an ureido terminated urethane compound as described above as a yellowing co-dyeing agent for spandex.
A fabric comprising the spandex described above.
The beneficial effects are that:
The carbamido terminated carbamate compound provided by the invention can be used as an additive for spandex spinning, can play a role in preventing yellow dyeing and avoiding dyeing chromatic aberration while improving the dye-uptake. Wherein, tertiary amine groups contained in the molecular structure can provide a dyeing seat of acid dye for spandex fiber, so that the dyeing property of the spandex is improved; meanwhile, the end part of the molecular structure contains urea groups, so that the effect of preventing spandex from yellowing can be achieved; the plurality of carbamate groups in the molecular structure can increase the solubility of the carbamate groups in the spinning solution and improve the anti-yellowing effect; limiting the length of the molecular structure can avoid the excessive concentration of groups, thereby increasing the uniformity of dyeing, increasing the proportion of anti-yellowing groups in the auxiliary agent, and avoiding the discoloration of dyed spandex.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the present invention are further described in detail by the following embodiments. In the interest of clarity and conciseness, not all features of an actual implementation are described in this specification.
Specifically, the invention provides an ureido-terminated carbamate compound, a preparation method and application thereof, wherein the structure of the ureido-terminated carbamate compound is shown as the following formula:
Wherein R 1 is an aliphatic structure having at least 1 carbon;
R 2 and R 3 are aliphatic structures having at least 2 carbons;
R 4 is an aliphatic structure, or an alicyclic structure containing at least one aliphatic ring, or an aromatic structure containing at least one benzene ring;
R 5 and R 6 are aliphatic structures having at least 1 carbon;
n≤5。
The compound provided by the invention can be used as an additive for spandex spinning, can play a role in preventing yellow dyeing and improving dyeing rate and simultaneously avoiding dyeing chromatic aberration. Wherein, a plurality of tertiary amine groups exist in the molecular structure, and the tertiary amine groups can be used as dye bases to react with the acid groups in the acid dye, so that the dyeing rate of spandex is improved. The molecular terminal contains hydrazine group, which can be oxidized and 'self-sacrificed' at higher temperature, and plays a certain role in protecting urea bond on polymer chain, thereby reducing degradation of polyurethane molecular chain, improving thermal degradation resistance and yellowing resistance, avoiding color change of polyurethane at high temperature shaping, and reducing chromatic aberration. However, the solvent adopted in the dry spinning of the spandex is usually DMAc, and the urea bond generated by the reaction of the hydrazine group and the isocyanate group is poor in solubility in the DMAc, so that the carbamate group is introduced into the molecular structure, the solubility of the carbamate group in the DMAc is good, the solubility of the anti-yellowing auxiliary agent in the spinning solution can be improved, the consumption can be increased, and the dyeing rate and the anti-yellowing capability of the spandex are further improved. The number of the circulating structures in the structural formula is limited to avoid enrichment of tertiary amine groups, namely, the mole number of the anti-yellowing auxiliary agent is increased under the condition that the dosage of the anti-yellowing auxiliary agent is certain, so that the anti-yellowing auxiliary agent can be more uniformly dispersed in a spinning solution, the dyeing uniformity is improved, and meanwhile, the proportion of hydrazine groups in the anti-yellowing auxiliary agent is increased, and the anti-yellowing capability is improved.
The invention also provides a preparation method of the compound, which comprises the following steps:
step 1): reacting the compound A with the compound B according to ase:Sub>A molar ratio of 1:2 to generate ase:Sub>A compound i with ase:Sub>A B-A-B structure;
step 2): reacting the compound C with the compound i according to ase:Sub>A molar ratio of 2:1 to generate an ureido terminated carbamate compound ii with ase:Sub>A C-B-A-B-C structure,
Wherein the structure of the compound A is shown as a formula (1),
In formula (1), R 1 is an aliphatic structure having at least 1 carbon, and R 2 and R 3 are aliphatic structures having at least 2 carbons;
The structure of the compound A contains tertiary amine groups and two terminal hydroxyl groups, R 1、R2 and R 3 are not particularly limited in the invention, so long as the structure of the formula (1) is satisfied, and preferable examples are N-methyldiethanolamine, N-ethyldiethanolamine and N-tertiary butyldiethanolamine.
The structure of the compound B is shown as a formula (2),
O=c=n-R 4 -n=c=o formula (2),
In the formula (2), R 4 is an aliphatic structure, or an alicyclic structure containing at least one aliphatic ring, or an aromatic structure containing at least one benzene ring;
the compound B is a diisocyanate, and MDI, TDI, HDI, IPDI and the like are preferable examples.
In the invention, the compound A and the compound B are dissolved in ase:Sub>A polar solvent according to the mol ratio of 1:2, then react for 2 hours at the temperature of 70-90 ℃ to obtain an intermediate product with ase:Sub>A B-A-B structure, namely ase:Sub>A compound i, the structure of the compound i is shown as ase:Sub>A formulase:Sub>A (3),
If the compound a and the compound B should react in a solvent and a bulk reaction is adopted, the product compound i in the step 1) is a solid, the reaction cannot be successfully completed, and the subsequent reaction cannot be performed.
As shown in the formula (3), the compound i is a compound blocked by isocyanate groups and contains tertiary amine groups and carbamate groups in the molecular chain, and in order to complete the reaction, a slight excess of the compound B containing isocyanate groups is provided to ensure that the product compound i is isocyanate-terminated. Alternatively, the molar ratio of compound a to compound B may be 1:2.05, preferably 1:2.1. In other alternative embodiments, the [ AB ] cycle structure may be present in the final product at a cycle number of 5 or less, and in such embodiments, the molar ratio of compound A to compound B may be from 1:1.2 to 1:2.1.
In the step 2), the compound C and the compound i prepared in the step 1) are reacted according to the mol ratio of 2:1 to generate the carbamide terminated carbamate compound ii with the C-B-A-B-C structure, wherein the structure of the compound C is shown as ase:Sub>A formulase:Sub>A (4),
In formula (4), R5 and R6 are aliphatic structures having at least 1 carbon.
Compound C is ase:Sub>A 1, 1-dialkylhydrazinocompound, ase:Sub>A preferred example being unsymmetrical dimethylhydrazine, and in step 2) the primary amino group of compound C is reacted with the isocyanate groups at both ends of compound i to link compound C to compound i to form the ureido-terminated urethane compound ii of the C-B-ase:Sub>A-B-C structure.
The reaction is completed in two steps instead of one step, the isocyanate end capped intermediate compound i with stable and uniform structure can be obtained in the first step, and then isocyanate groups at two ends of the intermediate compound i react with primary amine groups in the compound C, so that the product in the second step becomes ase:Sub>A C-B-A-B-C structure according to ase:Sub>A designed route, and the product with the structure contains two hydrazine groups, thereby having good anti-yellowing effect, and simultaneously contains two carbamate groups, having good solubility in polar solvents and being convenient for use in the spinning process. If all the raw materials are added at one time by adopting ase:Sub>A one-step method, structures such as C-B-C, C-B-A-B-A-B-A-B-A-B-C and the like may exist in the product, so that the product is nonuniform or the functional groups are too concentrated.
Correspondingly, the carbamido end capped carbamate compound prepared by the steps is used as an additive to be added into spandex spinning solution, so that the anti-yellowing dyeing-assisting effect can be achieved, and the anti-yellowing easy-dyeing spandex is prepared. The preparation method comprises the following specific steps:
Step a): mixing a dihydroxy compound with diisocyanate to react to obtain isocyanate terminated prepolymer;
Step b): dissolving the prepolymer obtained in the step a) in a solvent to prepare a prepolymer solution;
step c): after the prepolymer solution is cooled, carrying out chain extension reaction and chain termination reaction to obtain a spandex spinning solution;
Step d) adding the carbamido end capped carbamate compound auxiliary agent into the polyurethaneurea solution in the step c), and fully curing to obtain spinning solution;
and e) preparing the anti-yellowing easy-dyeing spandex fiber through dry spinning.
The carbamido terminated carbamate compound is used as a spinning auxiliary agent to be added into a spinning solution, the operation is simple and convenient, the chemical structure of spandex fiber is not changed, the influence on the performance of spandex is small, and simultaneously, better dyeing and anti-yellowing effects can be achieved.
For the gist of the present invention we will further describe in connection with the following series of examples.
Example 1
Step 1) dissolving N-methyldiethanolamine and MDI in DMAc according to a molar ratio of 1:2, and then reacting for 2 hours at 40 ℃ to generate a compound i with a structure shown as the following formula
Step 2) reacting a unsymmetrical dimethylhydrazine compound i at a molar ratio of 2:1 for 0.5h at 40 ℃ to produce an ureido terminated carbamate compound ii having the structure shown below,
Example 2
Step 1) dissolving N-tertiary butyl diethanol amine and MDI in DMAc according to a molar ratio of 2:1, and then reacting for 2 hours at 45 ℃ to generate a compound i with a structure shown as the following formula
Step 2) reacting the unsymmetrical dimethylhydrazine, MDI and the compound i for 0.5h at the temperature of 40 ℃ according to the mol ratio of 2:2:1 to generate the carbamide terminated carbamate compound ii with the structure shown as the following,
Example 3
Preparation of Huang Yiran polyurethane
Step a), mixing raw materials of polytetramethylene ether glycol PTMG 2000 and 4,4' -diphenylmethane diisocyanate, and reacting at 80 ℃ for 100min to prepare an isocyanate-terminated prepolymer;
Step b), cooling the prepolymer to 45 ℃, adding an N, N-dimethylacetamide solution, and uniformly stirring and mixing the mixture to prepare a prepolymer solution;
Step c) dissolving ethylenediamine and diethylamine into a solvent N, N-dimethylacetamide to form a mixed amine solution with the mass percent concentration of 7.00%, adding the prepared mixed amine solution into the N, N-dimethylacetamide solution of the prepolymer, and rapidly stirring to react to form a polyurethane solution with the mass percent concentration of 35%, wherein the molar ratio of amine groups to isocyanate groups is 1.04:1, a step of;
Step d) adding the carbamate auxiliary agent prepared in the example 1 into the polyurethane urea solution prepared in the step c), wherein the addition amount of the carbamate auxiliary agent is 1.5 percent of the weight of the spandex fiber, and storing the polyurethane urea solution at 45 ℃ for 40 hours, and fully curing the polyurethane urea solution to obtain a spinning solution;
and e) preparing the anti-yellowing easy-dyeing spandex fiber through dry spinning.
Example 4
Preparation of Huang Yiran polyurethane
Step a), mixing raw materials polytetramethylene ether glycol PTMG 1800, 4 '-diphenylmethane diisocyanate and 2,4' -diphenylmethane diisocyanate, and reacting at 90 ℃ for 120min to prepare an isocyanate group-terminated prepolymer;
Step b), cooling the prepolymer to 45 ℃, adding an N, N-dimethylacetamide solution, and uniformly stirring and mixing the mixture to prepare a prepolymer solution;
Step c) dissolving ethylenediamine, butanediamine and diethylamine into a solvent N, N-dimethylacetamide to form a mixed amine solution with the mass percent concentration of 7.00%, adding the prepared mixed amine solution into the N, N-dimethylacetamide solution of the prepolymer, and rapidly stirring to react to form a polyurethane solution with the mass percent concentration of 40%, wherein the molar ratio of amine groups to isocyanate groups is 1.04:1, a step of;
step d) adding the carbamate compound auxiliary agent prepared in the example 1 into the polyurethane urea solution prepared in the step c), wherein the addition amount of the carbamate compound auxiliary agent is 1.3% of the weight of the spandex fiber, and storing the polyurethane urea solution at 45 ℃ for 40 hours, and fully curing the polyurethane urea solution to obtain a spinning solution;
and e) preparing the anti-yellowing easy-dyeing spandex fiber through dry spinning.
Comparative example 1
Step a), mixing raw materials polytetramethylene ether glycol PTMG 1800, 4 '-diphenylmethane diisocyanate and 2,4' -diphenylmethane diisocyanate, and reacting at 90 ℃ for 120min to prepare an isocyanate group-terminated prepolymer;
Step b), cooling the prepolymer to 45 ℃, adding an N, N-dimethylacetamide solution, and uniformly stirring and mixing the mixture to prepare a prepolymer solution;
Step c) dissolving ethylenediamine, butanediamine and diethylamine into a solvent N, N-dimethylacetamide to form a mixed amine solution with the mass percent concentration of 7.00%, adding the prepared mixed amine solution into the N, N-dimethylacetamide solution of the prepolymer, and rapidly stirring to react to form a polyurethane solution with the mass percent concentration of 40%, wherein the molar ratio of amine groups to isocyanate groups is 1.04:1, a step of;
step d) preparing the common spandex fiber through dry spinning.
Anti-yellowing test:
10g of spandex fiber was placed in an oven at 200℃for 10 minutes, and the yellowness of the spandex fiber was measured using a fiber whiteness meter, and the measurement results are shown in the following table:
| sample name | Yellowness test L value | Yellowness test a value | Yellowness test b value |
| Example 3 | 83.6 | -4.60 | 8.23 |
| Example 4 | 81.2 | -4.79 | 9.76 |
| Comparative example 1 | 66.74 | 1.12 | 27.64 |
In the yellowness test result, L represents brightness, the value a represents the red-green value of the sample, the value a is larger than zero, the sample is reddish, and the value a is smaller than zero, the sample is greenish; the b value indicates that sample Huang Lanzhi, b is greater than zero and the sample is yellowish and less than zero and the sample is bluish. The redness and the yellowing are characterized by the color changed after the sample is oxidized, and the larger the numerical value is, the more serious the sample is oxidized, and the more serious the yellowing is.
As can be seen from the comparison of the data of the examples and the comparative examples, the yellowing resistance value is obviously reduced after the dyeing anti-yellowing auxiliary agent is added, and the better anti-yellowing effect is reflected.
Acid dye staining test:
Using acid dye to dye, using a spectrophotometer to test the concentration of dye molecules in dye liquor before and after dyeing, and determining the quality of dyeing effect according to the proportion of fewer dye molecules, wherein the proportion of dye molecules is defined as the dye uptake; and placing the dyed sample in soap solution for soaping, and measuring the concentration of dye molecules in the soap solution after soaping so as to characterize the difference of soaping fastness according to the proportion of the dye molecules left on the sample.
The data show that the addition of the dyeing anti-yellowing auxiliary is beneficial to the dyeing of dye molecules, the fixation of the dye molecules on spandex filaments, and the dyeing rate and soaping fastness of acid dye dyeing are improved.
Claims (10)
1. A process for the preparation of an ureido terminated urethane compound comprising the steps of:
step 1): reacting ase:Sub>A compound A with ase:Sub>A compound B according to ase:Sub>A molar ratio of 1:2 to generate an isocyanate-terminated compound i with ase:Sub>A B-A-B structure;
step 2): reacting the compound C with the compound i according to ase:Sub>A molar ratio of 2:1 to form an ureido terminated carbamate compound ii of the C-B-A-B-C structure,
Wherein the structure of the compound A is shown as a formula (1),
In formula (1), R 1 is methyl, ethyl or tert-butyl, R 2 and R 3 are ethyl;
The structure of the compound B is shown as a formula (2),
O=c=n-R 4 -n=c=o formula (2),
In formula (2), R 4 is a residue of MDI, TDI, HDI, IPDI other than an isocyanate group;
the structure of the compound i is shown as a formula (3),
The structure of the compound C is shown as a formula (4),
In formula 4, R 5 and R 6 are methyl groups.
2. The preparation method according to claim 1, wherein the reaction conditions of step 1) are specifically: compound a and compound B were dissolved in a polar solvent at a molar ratio of 1:2 and then reacted at a temperature of 35-50 ℃ for 2h.
3. The process according to claim 1, wherein the reaction conditions of step 2) are reaction at a temperature of 10-60 ℃ for 0.5h.
4. The method according to claim 1, wherein the compound a is at least one of N-methyldiethanolamine, N-ethyldiethanolamine, and N-t-butyldiethanolamine.
5. The preparation method according to claim 1, wherein the compound B is one or more of MDI, TDI, HDI, IPDI.
6. The preparation method according to claim 1, wherein the compound C is unsymmetrical dimethylhydrazine.
7. A preparation method of anti-yellowing easy-to-dye spandex is characterized in that an ureido-terminated carbamate compound is added into a spandex spinning solution, and the anti-yellowing easy-to-dye spandex is obtained after dry spinning, wherein the addition amount of the ureido-terminated carbamate compound is 0.1% -5% of the mass of spandex fiber;
the structure of the carbamido terminated carbamate compound is shown in the following formula:
Wherein R 1 is at least one of methyl, ethyl, or tert-butyl;
r 2 and R 3 are ethyl;
r 4 is one or more than one of the residues of MDI, TDI, HDI, IPDI except isocyanate groups;
R 5 and R 6 are methyl;
1≤n≤5。
8. the method for preparing anti-yellowing easy-to-dye spandex according to claim 7, wherein the preparation of spandex spinning solution comprises the following steps:
Step a): mixing a dihydroxy compound with diisocyanate to react to obtain isocyanate terminated prepolymer;
Step b): dissolving the prepolymer obtained in the step a) in a solvent to prepare a prepolymer solution;
step c): after the prepolymer solution is cooled, chain extension reaction and chain termination reaction are carried out to obtain the spandex spinning solution.
9. The method for preparing anti-yellowing and easy-to-dye spandex according to claim 7, wherein the addition amount of the carbamido-terminated carbamate compound is 0.1% -2% of the mass of the spandex fiber.
10. Use of the ureido-terminated urethane compound prepared by the preparation method of the ureido-terminated urethane compound as defined in any one of claims 1 to 6 as a yellowing-preventing dyeing assistant for spandex.
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