CN104829842B - Preparation method and application of silicon-containing dendritic-linear greasing agent - Google Patents
Preparation method and application of silicon-containing dendritic-linear greasing agent Download PDFInfo
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Abstract
The invention discloses a preparation method of silicon-containing dendritic-linear greasing agent, which comprises the steps that allyl glycidyl ether, end hydrogen-containing polysiloxane and chloroplatinic acid are added to a reactor, and undergo a reflux reaction; end ring alkoxy polysiloxane is obtained; end ring alkoxy polysiloxane reacts with acrylic acid to synthesize a functional polysiloxane long chain with epoxy radicals at one end and double bonds reserved at the other end; functional polysiloxane and first-generation polyamide-amine are added to the reactor and mixed, react, and then are purified; and the silicon-containing dendritic-linear greasing agent with functional groups is obtained. The silicon-containing dendritic-linear greasing agent can serve as a leather greasing agent in a leather greasing process; the prepared silicon-containing dendritic-linear greasing agent has the polysiloxane long chain and can endow leather with excellent flexibility, the reserved double bonds can further provide reactive groups, and facilitates performance optimization later; and an dendritic-linear structure has a certain filling effect, and can allow that the leather has good fullness and softness after applied to a product obtained by the leather greasing process.
Description
Technical field
The invention belongs to chemical technology field, the preparation and application of more particularly to a kind of siliceous dendroid-linear fatting agent.
Background technology
Polysiloxanes has a relatively low surface tension, excellent compliance and water vapor permeability, thus extensively application and leather
Process.And dendritic end-group functionality is big, high reactivity and also result in people's the advantages of branched structure
Extensive concern.Amino End Group polyamide-amide relative molecular mass is less, amino content is higher, and reaction is relatively active, therefore by control
Reaction condition and rate of charge can effectively adjust the speed of reaction and make reaction system promptly carry out graft reaction.
At present the fatting agent of synthesis is mostly the less linear fatting agent of linear structure or branch, due to its structure phase
To simple, single function, but for fatting agent development trend that is efficient, multi-functional, being firmly combined with, it is existing great majority this
The simple structure of class fatting agent is also difficult to meet these requirements.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of siliceous dendroid-linearly add
The preparation and application of fat agent, the method is simple to operate, and yield is high, can synthesize polysiloxane-grafted poly- with functional groups
The siliceous dendroid of amide-amine-linear fatting agent, in its molecular structure branch it is many, with amphipathic, be firmly combined with leather.
To achieve these goals, the technical solution used in the present invention is：
A kind of preparation method of siliceous dendroid-linear fatting agent, comprises the following steps：
Step one：Mol ratio is added to be 1 in reaction vessel:The end hydrogen containing siloxane of (2.0～2.3) and pi-allyl contract
Water glycerin ether, and catalyst chloroplatinic acid and the first solvent are added, rear temperature rising reflux is well mixed, except the solvent of dereaction first, carry
Both-end epoxy radicals polysiloxanes is obtained after pure；
Step 2：In molar ratio (1.0～1.3)：1 mixes acrylic acid with the both-end epoxy radicals polysiloxanes, and adds
Enter catalyst TBAB and the first solvent, be well mixed rear temperature rising reflux, remove reaction dissolvent, carried after purification
The polysiloxanes of functional groups；
Step 3：It is in molar ratio 1 under nitrogen protective condition:(0.8～1) is by a PAMAM and described carries
The polysiloxanes of functional groups is added in reactor, and adds the second solvent, and stirring is reacted, and reaction is purified after terminating
Obtain siliceous dendroid-linear polymer.
The quality of the chloroplatinic acid added in the step one is end hydrogen containing siloxane and the total matter of allyl glycidyl ether
Amount 0.15～0.35%, reaction temperature be 90～110 DEG C, the reaction time be 4～6h, first solvent be toluene, toluene
Addition there is no occurrence, act primarily as regulation reaction system viscosity, beneficial to reaction effect.
What is purified in the step one concretely comprises the following steps：Vacuum filtration removes reaction dissolvent toluene and mistake at 70～90 DEG C
The allyl glycidyl ether of amount.
The quality of the TBAB added in the step 2 is epoxy terminated polysiloxanes and acrylic acid gross mass
0.4～0.6%, reaction temperature be 100～120 DEG C, the reaction time be 6～9h, first solvent be toluene, toluene plus
Entering amount does not have occurrence, regulation reaction system viscosity is acted primarily as, beneficial to the effect of reaction.
The second solvent is isopropanol or methyl alcohol in the step 3, and reaction temperature is 50～80 DEG C, the reaction time is 4～
6h。
What is purified in the step 3 concretely comprises the following steps：First vacuum filtration removes reaction dissolvent isopropanol at 40～60 DEG C
Or methyl alcohol obtains crude product, then crude product is dissolved in saturated aqueous common salt, layering remove have neither part nor lot in reaction with both-end alkene
The polysiloxanes of base functional groups, is then extracted with ether, takes ether layer, and then reduce pressure suction filtration, in triplicate, is removed not anti-
The PAMAM answered.
Siliceous dendroid obtained by of the invention-linear fatting agent can be used in leather greasing operation as leather fat,
Concrete technology is as follows：Wet blue leather shaving is weighed, and in rotary drum, after chrome retanned, neutralization to PH is 5.5～6.0, is subsequently adding blue wet
The siliceous dendroid of leather mass fraction 10～20%-linear fatting agent, liquor ratio 1：1, in rotary drum transfer 2h at 55 DEG C, after can press
Conventional leather goods produce and process process operations.
Compared with prior art, the preparation method of the siliceous dendroid that the present invention is provided-linear fatting agent, synthesizes first
Then one end utilizes in a mild condition epoxy radicals with polysiloxanes long-chain of the epoxy radicals other end with feature thiazolinyl
With amino reaction, the polysiloxane-grafted to dendritic interphase of the periphery containing many Amino End Groups of feature thiazolinyl will be carried
On, finally synthesize a kind of novel siliceous fatting agent with functional groups with special dendroid-linear structure.The present invention with
Allyl glycidyl ether, end hydrogen containing siloxane, chloroplatinic acid, acrylic acid, TBAB, a PAMAM are original
Material, because these material toxicities are low, biocompatibility is high, excellent performance, therefore, the present invention has the little, synthetic method of pollution simple
List and target product have the advantages that several functions.
Secondly, the siliceous dendroid that the present invention is provided-linear fatting agent, in the end group of Amino End Group dendritic macromole
On introduce the polysiloxanes long-chain with functional groups, siloxanes long-chain can give leather splendid submissive performance, and double bond can
Reactive group is provided for further optimization product.At the same time the hydrophobic grouping of long-chain, the parent with dendritic macromole periphery
Water amino can be formed a kind of branch it is more, with amphipathic dendroid-linear polymer fatting agent.Using dendritic macromole
The hydrophily of upper Amino End Group and the hydrophobicity of long-chain, use conventional methods and are allowed to be penetrated into intracutaneous.Due to siliceous dendroid-
The hydrophilic characteristic of the multiterminal of linear fatting agent so as to hydrogen bond occurs by the active site on leather fiber macromolecular chain or chemistry is made
With, remain between leather fiber, it is difficult to be washed out by water or solvent, it is firmly combined with leather.And the present invention is former by optimizing
Material composition and proportioning and reaction condition, by the siliceous dendroid prepared-linear fatting agent leather greasing operation is applied to, can
Give leather excellent soft and full property.
Specific embodiment
The preparation method of the siliceous dendroid provided the present invention with reference to embodiment-linear fatting agent is made further in detail
Describe in detail bright.
Embodiment one
A kind of preparation method of siliceous dendroid-linear fatting agent, comprises the following steps：
Step one：Mol ratio is added to be 1 in reaction vessel:2.1 end hydrogen containing siloxane and allyl glycidol
Ether, and the solvent toluene of the catalyst chloroplatinic acid of reactant gross mass 0.15% and excess is added, 90 are warming up to after being well mixed
DEG C back flow reaction 4h, vacuum filtration removes the allyl glycidyl ether of reaction dissolvent toluene and excess at 70～90 DEG C, obtains
To epoxy terminated polysiloxanes.
Step 2：In molar ratio 1：1.1 by the both-end epoxy radicals polysiloxanes of above-mentioned synthesis and acrylic acid and solvent toluene
In adding reaction vessel, add solvent toluene and account for the TBAB catalyst of reactant gross mass 0.6%, will be above-mentioned anti-
Answer system in 100 DEG C of back flow reactions 6h, solvent toluene is removed afterwards, obtain the polysiloxanes with functional groups.
Step 3：It is in molar ratio 1 under conditions of nitrogen protection:1 by a PAMAM and with feature base
The polysiloxanes of group is added in reactor, and adds solvent isopropanol, reaction 5h is stirred at 60 DEG C, afterwards first 40
Vacuum filtration removes reaction dissolvent isopropanol at～60 DEG C, and then crude product is dissolved in saturated aqueous common salt, and layering is removed not to be joined
With the polysiloxanes with both-end thiazolinyl functional groups for reacting so, extracted with ether after, take ether layer, then decompression is taken out
Filter, in triplicate, by aforesaid operations a unreacted PAMAM is removed.Finally give siliceous dendroid-linear stuffing
Agent.
Step 4：By the siliceous dendroid linear polymer application of above-mentioned synthesis and leather greasing operation, technique for applying is such as
Under：Wet blue leather shaving is weighed, and in rotary drum, after chrome retanned, neutralization to PH is 5.5～6.0, is subsequently adding wet blue leather mass fraction
10～20% siliceous dendroid-linear fatting agent, liquor ratio 1：1, in rotary drum transfer 2h at 55 DEG C, after can be by conventional leather goods
Production and processing process operations.
Embodiment two：
A kind of preparation method of siliceous dendroid-linear fatting agent, comprises the following steps：
Step one：Mol ratio is added to be 1 in reaction vessel:2.3 end hydrogen containing siloxane and allyl glycidol
Ether, and the solvent toluene of the catalyst chloroplatinic acid of reactant gross mass 0.2% and excess is added, 90 DEG C are warming up to after being well mixed
Back flow reaction 6h, vacuum filtration removes the allyl glycidyl ether of reaction dissolvent toluene and excess at 70～90 DEG C, obtains
Epoxy terminated polysiloxanes.
Step 2：In molar ratio 1：1.1 by the both-end epoxy radicals polysiloxanes of above-mentioned synthesis and acrylic acid and solvent toluene
In adding reaction vessel, add solvent toluene and account for the TBAB catalyst of reactant gross mass 0.6%, will be above-mentioned anti-
Answer system in 100 DEG C of back flow reactions 6h, solvent toluene is removed afterwards, obtain the polysiloxanes with functional groups.
Step 3：It is in molar ratio 1 under conditions of nitrogen protection:1 by a PAMAM and with feature base
The polysiloxanes of group is added in reactor, and adds solvent methanol, and reaction 5h is stirred at 60 DEG C, afterwards first 40～
Vacuum filtration removes reaction dissolvent methyl alcohol at 60 DEG C, and then crude product is dissolved in saturated aqueous common salt, and layering removing has neither part nor lot in instead
The polysiloxanes with both-end thiazolinyl functional groups answered so, after extracted with ether, take ether layer, then reduce pressure suction filtration, weight
It is multiple three times, remove a unreacted PAMAM by aforesaid operations.Finally give siliceous dendroid-linear fatting agent.
Step 4：By the siliceous dendroid linear polymer application of above-mentioned synthesis and leather greasing operation.Technique for applying is such as
Under：Wet blue leather shaving is weighed, and in rotary drum, after chrome retanned, neutralization to PH is 5.5～6.0, is subsequently adding wet blue leather mass fraction
10～20% siliceous dendroid-linear fatting agent, liquor ratio 1：1, in rotary drum transfer 2h at 55 DEG C, after can be by conventional leather goods
Production and processing process operations.
Embodiment three：
A kind of preparation method of siliceous dendroid-linear fatting agent, comprises the following steps：
Step one：Mol ratio is added to be 1 in reaction vessel:2.3 end hydrogen containing siloxane and allyl glycidol
Ether, and the solvent toluene of the catalyst chloroplatinic acid of reactant gross mass 0.2% and excess is added, 90 DEG C are warming up to after being well mixed
Back flow reaction 6h, vacuum filtration removes the allyl glycidyl ether of reaction dissolvent toluene and excess at 70～90 DEG C, obtains
Epoxy terminated polysiloxanes.
Step 2：In molar ratio 1：1.3 by the both-end epoxy radicals polysiloxanes of above-mentioned synthesis and acrylic acid and solvent toluene
In adding reaction vessel, add solvent toluene and account for the TBAB catalyst of reactant gross mass 0.65%, will be above-mentioned
Reaction system removes afterwards solvent toluene in 120 DEG C of back flow reactions 8h, obtains the polysiloxanes with functional groups.
Step 3：It is in molar ratio 1 under conditions of nitrogen protection:1 by a PAMAM and with feature base
The polysiloxanes of group is added in reactor, and adds solvent isopropanol, reaction 5h is stirred at 60 DEG C, afterwards first 40
Vacuum filtration removes reaction dissolvent isopropanol at～60 DEG C, and then crude product is dissolved in saturated aqueous common salt, and layering is removed not to be joined
With the polysiloxanes with both-end thiazolinyl functional groups for reacting so, extracted with ether after, take ether layer, then decompression is taken out
Filter, in triplicate, by aforesaid operations a unreacted PAMAM is removed.Finally give siliceous dendroid-linear stuffing
Agent.
Step 4：By the siliceous dendroid linear polymer application of above-mentioned synthesis and leather greasing operation.Technique for applying is such as
Under：Wet blue leather shaving is weighed, and in rotary drum, after chrome retanned, neutralization to PH is 5.5～6.0, is subsequently adding wet blue leather mass fraction
10～20% siliceous dendroid-linear fatting agent, liquor ratio 1：1, in rotary drum transfer 2h at 55 DEG C, after can be by conventional leather goods
Production and processing process operations.
Example IV：
A kind of preparation method of siliceous dendroid-linear fatting agent, comprises the following steps：
Step one：Mol ratio is added to be 1 in reaction vessel:2.1 end hydrogen containing siloxane and allyl glycidol
Ether, and the solvent toluene of the catalyst chloroplatinic acid of reactant gross mass 0.15% and excess is added, 90 are warming up to after being well mixed
DEG C back flow reaction 6h, vacuum filtration removes the allyl glycidyl ether of reaction dissolvent toluene and excess at 70～90 DEG C, obtains
To epoxy terminated polysiloxanes.
Step 2：In molar ratio 1：1.3 by the both-end epoxy radicals polysiloxanes of above-mentioned synthesis and acrylic acid and solvent toluene
In adding reaction vessel, add solvent toluene and account for the TBAB catalyst of reactant gross mass 0.65%, will be above-mentioned
Reaction system removes afterwards solvent toluene in 120 DEG C of back flow reactions 8h, obtains the polysiloxanes with functional groups.
Step 3：It is in molar ratio 1 under conditions of nitrogen protection:0.8 by a PAMAM and with feature
The polysiloxanes of group is added in reactor, and adds solvent isopropanol, and reaction 5h is stirred at 70 DEG C, is first existed afterwards
Vacuum filtration removes reaction dissolvent isopropanol at 40～60 DEG C, and then crude product is dissolved in saturated aqueous common salt, and layering is removed not
Participate in the polysiloxanes with both-end thiazolinyl functional groups of reaction so, after extracted with ether, take ether layer, then decompression is taken out
Filter, in triplicate, by aforesaid operations a unreacted PAMAM is removed.Finally give siliceous dendroid-linear stuffing
Agent.
Step 4：By the siliceous dendroid linear polymer application of above-mentioned synthesis and leather greasing operation.Technique for applying is such as
Under：Wet blue leather shaving is weighed, and in rotary drum, after chrome retanned, neutralization to PH is 5.5～6.0, is subsequently adding wet blue leather mass fraction
10～20% siliceous dendroid-linear fatting agent, liquor ratio 1：1, in rotary drum transfer 2h at 55 DEG C, after can be by conventional leather goods
Production and processing process operations.
Shown in the preparation technology principle and the following reaction equation of process of the present invention：
The siliceous dendroid prepared with the present invention-linear fatting agent agent is processed leather, and its every result is respectively such as
Shown in table 1.
Table 1
Table 1 is siliceous dendroid in embodiment one-linear fatting agent to leather sample properties testing result after stuffing.
It has been observed that after siliceous dendroid-linear fatting agent is applied to into leather greasing operating, physical and mechanical properties has and changes
Kind, particularly pliability is obviously improved.The above results show, siliceous dendroid-linear fatting agent is applied to into currier
In sequence, good application effect is obtained, has given leather splendid softness.
Claims (8)
1. the preparation method of a kind of siliceous dendroid-linear fatting agent, it is characterised in that comprise the following steps：
Step one：Mol ratio is added to be 1 in reaction vessel:The end hydrogen containing siloxane of (2.0～2.3) and allyl glycidyl are sweet
Oily ether, and catalyst chloroplatinic acid and the first solvent are added, rear temperature rising reflux is well mixed, except the solvent of dereaction first, after purification
Obtain both-end epoxy radicals polysiloxanes；
Step 2：In molar ratio (1.0～1.3)：1 mixes acrylic acid with the both-end epoxy radicals polysiloxanes, and addition is urged
Agent TBAB and the first solvent, are well mixed rear temperature rising reflux, remove reaction dissolvent, obtain with functional after purification
The polysiloxanes of property group；
Step 3：It is in molar ratio 1 under nitrogen protective condition:(0.8～1) is by a PAMAM and described with functional
Property group polysiloxanes be added in reactor, and add the second solvent, stirring is reacted, and reaction is purified after terminating and obtained
Siliceous dendroid-linear polymer.
2. the preparation method of siliceous dendroid-linear fatting agent according to claim 1, it is characterised in that the step one
The quality of the chloroplatinic acid of middle addition is hold hydrogen containing siloxane and allyl glycidyl ether gross mass 0.15～0.35%, instead
Temperature is answered for 90～110 DEG C, the reaction time is 4～6h, first solvent is toluene.
3. the preparation method of siliceous dendroid-linear fatting agent according to claim 1, it is characterised in that the step one
Middle purification is concretely comprised the following steps：Vacuum filtration removes the allyl glycidol of reaction dissolvent toluene and excess at 70～90 DEG C
Ether.
4. the preparation method of siliceous dendroid-linear fatting agent according to claim 1, it is characterised in that the step 2
The quality of the TBAB of middle addition is the 0.4～0.6% of epoxy terminated polysiloxanes and acrylic acid gross mass, reaction temperature
Spend for 100～120 DEG C, the reaction time is 6～9h, first solvent is toluene.
5. the preparation method of siliceous dendroid-linear fatting agent according to claim 1, it is characterised in that the step 3
In the second solvent be isopropanol or methyl alcohol, reaction temperature is 50～80 DEG C, and the reaction time is 4～6h.
6. the preparation method of siliceous dendroid-linear fatting agent according to claim 1, it is characterised in that the step 3
Middle purification is concretely comprised the following steps：First vacuum filtration removes reaction dissolvent and obtains crude product at 40～60 DEG C, then by crude product
In being dissolved in saturated aqueous common salt, layering removes the polysiloxanes with both-end thiazolinyl functional groups for having neither part nor lot in reaction, Ran Houyong
Ether is extracted, and takes ether layer, and then reduce pressure suction filtration, in triplicate, removes a unreacted PAMAM.
7. a kind of siliceous dendroid of claim 1 gained-linear fatting agent in leather greasing operation as leather fat
Using.
8. apply according to claim 7, it is characterised in that technique for applying is as follows：Wet blue leather shaving is weighed, in rotary drum,
After chrome retanned, neutralization to PH is 5.5～6.0, be subsequently adding the siliceous dendroid of wet blue leather mass fraction 10～20%-linear plus
Fat agent, liquor ratio 1：1, in rotary drum transfer 2h at 55 DEG C, after can by conventional leather goods produce and process process operations.
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| WO2017094392A1 (en) * | 2015-12-04 | 2017-06-08 | 信越化学工業株式会社 | Linear organopolysiloxane having different functional groups at both terminals, and method for producing same |
| JP2017105753A (en) * | 2015-12-04 | 2017-06-15 | 信越化学工業株式会社 | Straight chain organopolysiloxane having different functional group at both terminal, and method of producing the same |
| CN110713604B (en) * | 2019-10-14 | 2021-07-13 | 浙江海洋大学 | Preparation method of PAMAM composite antifouling material |
| CN112679681B (en) * | 2020-12-23 | 2022-06-03 | 齐河力厚化工有限公司 | Organic silicon polymer and preparation method and application thereof |
| CN115434044B (en) * | 2022-11-07 | 2023-03-24 | 江苏恒力化纤股份有限公司 | Solvent-free bi-component spinning oil agent and preparation method and application thereof |
| CN116333563B (en) * | 2023-04-25 | 2024-01-26 | 福建三青涂料有限公司 | Crystal brick waterproof composition |
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