CN103214676B - A kind of terpolymer block silicone oil synthetic method - Google Patents
A kind of terpolymer block silicone oil synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of terpolymer block silicone oil synthetic method, each Ingredient Amount is in mass parts: A, add 100 parts of dimethicone or octamethylcyclotetrasiloxane, the agent of 4 parts of end ring oxygen double-seal heads, 15 parts of N,N-DIMETHYLACETAMIDEs, be warming up to 70-80 DEG C, add 0.02-0.1 part alkaline catalysts, be warming up to 110-120 DEG C, reaction 3-4h, slowly open vacuum, extract solvent and low molecular weight substance out, keep being warming up to 140-145 DEG C, be incubated and keep vacuum 2h, obtaining end epoxy silicon oil; B, add epoxy-terminated silicone oil 80-100 part, polyether glycol 6-30 part, Virahol 150 parts, back flow reaction 6-15h at 8O-86 DEG C, removed under reduced pressure Virahol or add propylene glycol replacement solvent, obtain amino-polyether block silicone oil.Fabric uses the good hand touch after tri-block copolymerization silicone oil of the present invention, i.e. fluffy sense, and smooth feeling, fabric is without xanthochromia or low-yellowing.
Description
Technical field
The present invention relates to a kind of synthetic method of modified silicon oil, be specially terpolymer block silicone oil synthetic method.
Background technology
At present, be widely used in the Final finishing processing of the textiless such as cotton, silk, wool and terylene based on the softening agent of various amino-modified silicone oil emulsion, the fabric of arrangement has softness, performance smooth, attractive in appearance, washable and comfortable and easy to wear.This series products accept by people.It is hydrophobicity that weak point is mainly manifested in the fabric arranged through it, feels sultry and be difficult to washing when wearing; The light color arranged with it and white fabrics, after baking through high temperature, there will be Yellowing in various degree, the stability of a lot of amido-modified silicone microemulsion is very poor, occurs " breakdown of emulsion floating oil " phenomenon in be everlasting accumulating and application process; Roll banding phenomenon is had to produce padding in use procedure.
In order to overcome the above-mentioned shortcoming of traditional amido silicon oil, people adopt various method to improve, and have pendant polyether modification, also have epoxide modified or carboxy-modified, modified silicone oil stability to improve, but feel deviation.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of terpolymer block silicone oil synthetic method, the terpolymer block silicone oil obtained by the method.
Technical scheme of the present invention: for solving the problems of the technologies described above, terpolymer block silicone oil synthetic method of the present invention in turn includes the following steps, and each Ingredient Amount calculates with mass parts:
A, in reaction vessel, add 100 parts of dimethicone or octamethylcyclotetrasiloxane, the agent of 4 parts of end ring oxygen double-seal heads, 15 parts of N,N-DIMETHYLACETAMIDEs, be warming up to 70-80 DEG C, add 0.02-0.1 part alkaline catalysts, be warming up to 110-120 DEG C again, reaction 3-4h, then slowly opens vacuum, extract solvent and low molecular weight substance out, and keep being warming up to 140-145 DEG C, be incubated and keep vacuum 2h, obtaining holding epoxy silicon oil;
B, in reaction vessel, add epoxy-terminated silicone oil 80-100 part obtained by steps A, polyether glycol 6-30 part, Virahol 150 parts, carries out back flow reaction 6-15h at 8O-86 DEG C, last removed under reduced pressure Virahol or add propylene glycol replacement solvent, obtains amino-polyether block silicone oil.
Further, alkaline catalysts described in steps A is potassium hydroxide.
Further, polyether glycol described in step B is made up of 2-10 part polyether glycol 203,2-10 part polyether glycol 206 and 2-10 part polyether glycol 209.
Further, the end ring oxygen double-seal head agent described in steps A is prepared by following substances, and each material consumption calculates with mass parts:
The tetramethyl-dihydro base sily oxide of 35 parts of hydrogeneous double-seal heads, 42 parts of glycidyl allyl ethers, 100 parts of N,N-DIMETHYLACETAMIDEs are added in withstand voltage reactor, stir, add 1 part of 1%(quality) Platinic chloride ethanolic soln, then capping still, be warming up to 90-95 DEG C of reaction 7-8h, finally by reactant underpressure distillation, except desolventizing obtains the agent of end ring oxygen double-seal head.
Tri-block copolymerization silicone oil of the present invention not only has high temperatures, without breakdown of emulsion demixing phenomenon, the advantages such as self-emulsifying properties, and owing to carrying out amino and the copolymerization of polyether-based linearity block in siloxane backbone, synthesize new linear amino-polyether group block copolymer, namely tri-block copolymerization silicone oil is due to the anchorage effect of amino, make whole polysiloxane energy mortise at fabric face, maintain the original flexible smooth of polysiloxane, hydrophilic polyether segment is then present in fiber surface to fall the form of shape, water molecules is in the uncrossed transmission of fiber surface, form soft and hydrophilic compatibility, this is a new stage of silicone softening agent development, also be following developing direction.The smooth feeling of general tri-block copolymerization silicone oil is all fine, and fluffy sense is just carried out not too easily, and the end epoxy silicon oil intermediate synthesized by the present invention can bring very large adjustment leeway to later reaction, ensure that fluffy sense.Relate to following two aspects in present invention process process to regulate: the end ring oxygen silicone molecule amount size one, regulating synthesis; Two, polyethers kind and consumption is regulated, thus the feel skewed popularity of adjustment fabric.Generally speaking, fabric uses the good hand touch after tri-block copolymerization silicone oil of the present invention, i.e. fluffy sense, and smooth feeling, fabric is without xanthochromia or low-yellowing.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiments of the invention 1:
General thought of the present invention is: first will hold containing hydrogen silicone oil and glycidyl allyl ether under platinum catalysis, carry out siloxanes end hydrogen bond and the addition reaction of carbon double bond generates end ring oxygen double-seal head (also can be commercially available end ring oxygen double-seal head), then by end ring oxygen double-seal head and D4(octamethylcyclotetrasiloxane) or DMC(dimethicone) ring-opening polymerization becomes to hold epoxy silicon oil, then, by affixture under solvent condition with polyether reactant condensation.Reaction formula is as follows:
。
Concrete reactions steps of the present invention is as follows:
A, in 250ml there-necked flask, add 100gDMC (dimethicone) or D4(octamethylcyclotetrasiloxane); Add the agent of 4g end ring oxygen double-seal head; Add 15 parts of N,N-DIMETHYLACETAMIDEs again, be warming up to 70-80 DEG C, add 0.02-0.1g potassium hydroxide as alkaline catalysts; Then be warming up to 110-120 DEG C of reaction 3-4h, then slowly open vacuum, solvent and low molecular weight substance are extracted out, and keep being warming up to 140-145 DEG C, insulation vacuumizes 2h, obtains holding epoxy silicon oil.
B, in 500ml there-necked flask, add above-mentioned epoxy-terminated silicone oil: 80-100g, polyether glycol 203:2-10g, polyether glycol 206:2-10g, polyether glycol 209:2-10g, Virahol: 150g, DEG C back flow reaction 6-15h is carried out in 8O ~ 86, last removed under reduced pressure Virahol or add propylene glycol replacement solvent, obtains the amino-polyether block silicone oil that outward appearance is pale yellow transparent, i.e. tri-block copolymerization silicone oil.
Wherein, namely polyether glycol 203 refers to containing Liang Ge functional group, and molecular weight is the polyether glycol of 300, polyether glycol 206 refers to containing Liang Ge functional group, molecular weight is the polyether glycol of 600, and polyether glycol 209 refers to that molecular weight is the polyether glycol of 900 containing Liang Ge functional group.
End ring oxygen double-seal head agent used adopts commercially available product or is prepared by following substances, and each material consumption calculates with mass parts:
The tetramethyl-dihydro base sily oxide of 35 parts of hydrogeneous double-seal heads, 42 parts of glycidyl allyl ethers, 100 parts of N,N-DIMETHYLACETAMIDEs are added in withstand voltage reactor, stir, add 1 part of 1%(quality) Platinic chloride ethanolic soln, then capping still, be warming up to 90-95 DEG C of reaction 7-8h, finally by reactant underpressure distillation, except desolventizing obtains the agent of end ring oxygen double-seal head.
Embodiments of the invention 2:A step and all the other are with embodiment 1, do not repeat, difference is: at reactions steps B, the epoxy-terminated silicone oil of step A gained is added: 90g in 500ml there-necked flask, polyether glycol 203:5g, polyether glycol 206:2.5g, polyether glycol 209:2.5g, Virahol: 150g, back flow reaction 12h is carried out at 80 DEG C, last removed under reduced pressure Virahol or add propylene glycol replacement solvent, obtain the amino-polyether block silicone oil that outward appearance is pale yellow transparent, i.e. tri-block copolymerization silicone oil.
Claims (1)
1. a terpolymer block silicone oil synthetic method, it is characterized in that this synthetic method comprises following reactions steps, each Ingredient Amount calculates with mass parts:
A, in reaction vessel, add 100 parts of dimethicone or octamethylcyclotetrasiloxane, the agent of 4 parts of end ring oxygen double-seal heads, 15 parts of N,N-DIMETHYLACETAMIDEs, be warming up to 70-80 DEG C, add 0.02-0.1 part potassium hydroxide, be warming up to 110-120 DEG C again, reaction 3-4h, then slowly opens vacuum, extract solvent and low molecular weight substance out, keep being warming up to 140-145 DEG C, be incubated and keep vacuum 2h, obtain holding epoxy silicon oil;
B, in reaction vessel, add epoxy-terminated silicone oil 90 parts obtained by steps A, polyether glycol 10 parts, Virahol 150 parts, carries out back flow reaction 12h at 80 DEG C, last removed under reduced pressure Virahol or add propylene glycol replacement solvent, obtains amino-polyether block silicone oil;
Wherein polyether glycol described in step B is made up of 5 parts of polyether glycols, 203,2.5 parts of polyether glycols 206 and 2.5 parts of polyether glycols 209;
The agent of end ring oxygen described in described steps A two envelope is prepared by following substances, each material consumption calculates with mass parts: in withstand voltage reactor, add the tetramethyl-dihydro base sily oxide of 35 parts of hydrogeneous double-seal heads, 42 parts of glycidyl allyl ethers, 100 parts of N,N-DIMETHYLACETAMIDEs, stir, add the Platinic chloride ethanolic soln of 1 part 1% (quality), then capping still, be warming up to 90-95 DEG C of reaction 7-8h, finally by reactant underpressure distillation, except desolventizing obtains the agent of end ring oxygen double-seal head.
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| CN113861427A (en) * | 2021-08-16 | 2021-12-31 | 广东传化富联精细化工有限公司 | Preparation of hydrophilic silicone oil for cotton with high bubble fastness |
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Denomination of invention: A Synthesis Method of Ternary Copolymer Block Silicone Oil Effective date of registration: 20221010 Granted publication date: 20150826 Pledgee: China Guangfa Bank Co.,Ltd. Shaoxing Branch Pledgor: Zhejiang jiefa Technology Co.,Ltd. Registration number: Y2022980017885 |
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