CN103073568B - The preparation method of 1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane - Google Patents
The preparation method of 1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane Download PDFInfo
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- CN103073568B CN103073568B CN201210238655.3A CN201210238655A CN103073568B CN 103073568 B CN103073568 B CN 103073568B CN 201210238655 A CN201210238655 A CN 201210238655A CN 103073568 B CN103073568 B CN 103073568B
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Abstract
The invention discloses the preparation method of a kind of 1,3 diglycidyl ether epoxide propyl group 1,1,3,3 tetramethyl disiloxanes, it is characterised in that by allyl glycidyl ether and 1,1,3,3 tetramethyl disiloxane additive reaction gained.The preparation method of the amino-polyether silicone oil in the present invention: yield is up to 98%, the utilization of resources has reached to maximize；Without using the acidic materials such as sulphuric acid to make catalyst, without dangerous, production process safety；Production process will not produce solid waste.
Description
Technical field
The present invention relates to the preparation side of a kind of 1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane
Method, the preparation method of amino-polyether block silicone oil and softening agent.
Background technology
Textile softener more than 90% in the market is amido silicon oil.Fabric sofetening, cunning through amido silicon oil process
Refreshing, fluffy, bullet very, crease-resistant, be the maximum textile auxiliary of current consumption, be referred to as the king of softening agent.It is by N-2-ammonia second
Base-3-aminopropyltriethoxy dimethoxysilane coupling agent (i.e. KBM-602) and prestox ring tetrasilane (i.e. D4) polymerisation in bulk shape
Become, due on its side chain containing 2 amino, there is its own shortcomings aborning:
(1) under light, hot effect, easy yellowing；
(2) natural fiber loses hydrophilic, and effect is taken in impact；
(3) it is difficult to peel off from fabric, affects resisdye and the Xiu Se of fabric；
(4) easy breakdown of emulsion under the process conditions such as high temperature, alkaline agent, high shear force, makes fabric produce " oil mark "；
(5) there is the phenomenon such as roll banding, viscous cylinder.
For overcoming disadvantages mentioned above, exploitation a new generation's low-yellowing and hydrophilic softener become the development of domestic and international auxiliary industry
Direction.Organosilicon worker is devoted to find new silane coupler to substitute KBM-602, in practice it has proved that can select piperazine
The silane couplers such as base, piperidyl, morpholinyl produce amido silicon oil, but use above-mentioned silane coupler or can only solve portion
Point problem, or reduce flexibility while overcoming disadvantages mentioned above.
Summary of the invention
An object of the present invention is to overcome deficiency of the prior art, it is provided that a kind of 1,3-diglycidyl ether oxygen
The preparation method of base propyl group-1,1,3,3 tetramethyl disiloxane.
For achieving the above object, the present invention is realized by techniques below means:
1,3-diglycidyl ether epoxide propyl group-1, the preparation method of 1,3,3 tetramethyl disiloxane, it is characterised in that
By allyl glycidyl ether and 1,1,3,3-tetramethyl disiloxane additive reaction gained.
Preferably, allyl glycidyl ether and 1,1,3,3-tetramethyl disiloxane reacts under catalyst action.
Preferably, described catalyst amount is and allyl glycidyl ether and 1, and 1,3,3-tetramethyl disiloxane is used
The ratio of amount sum is 10～30ppm.
Preferably, described catalyst includes being coordinated rhodium catalyst and one or more in coordination platinum catalyst.
Described coordination rhodium catalyst includes but not limited to triphenylphosphine radium chloride.
Described coordination platinum catalyst includes but not limited to that methyl vinyl silicone coordination platinum, the platinum of oxolane coordination are urged
One or more in the platinum of agent and diethyl phthalate coordination.
Preferably, described coordination rhodium catalyst is (0.5～2) with the weight ratio of coordination platinum catalyst: 1.
Preferably, reaction temperature is 50 DEG C～70 DEG C.
The two of the purpose of the present invention are to overcome deficiency of the prior art, it is provided that a kind of amino-polyether block silicone oil
Preparation method.
For achieving the above object, the present invention is realized by techniques below means:
The preparation method of a kind of amino-polyether block silicone oil, it is characterised in that gathered with amino by epoxy-capped polysiloxanes
Ether reaction obtains.
Preferably, described amino-polyether block silicone oil structural formula is:
Described a is in the range of (0～20)；B is in the range of (0～25)；N is in the range of (0～200)；Described amino-polyether
Molecular weight be 100～3000.
Described amino-polyether is selected from ED-600, ED-900, ED-2003 of Huntsman company.
Epoxy-capped polysiloxanes is 60:40～95:5 with the weight ratio of amino-polyether.
Preferably, epoxy-capped polysiloxanes by 1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl two silicon
Oxygen alkane and the reaction of prestox ring tetrasilane obtain；The structural formula of epoxy-capped polysiloxanes is:
CH2CH(O) CH2OC3H6Me2SiO(Me2SiO) nMe2SiC3H6OCH2(O) CHCH2。
1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane and the weight of prestox ring tetrasilane
Than being (1～15): (99～85).
Preferably, described 1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane is contracted by pi-allyl
Water glycerin ether and 1,1,3,3-tetramethyl disiloxane additive reaction gained.
Preferably, allyl glycidyl ether and 1,1,3,3-tetramethyl disiloxane reacts under catalyst action.
Preferably, described catalyst amount is allyl glycidyl ether and 1,1,3,3-tetramethyl disiloxane consumption
The ratio of sum is 10～30ppm, i.e. catalyst weight is allyl glycidyl ether and 1,1,3,3-tetramethyl disiloxane weight
The 100000 of amount sum/to 3/100000ths.
Preferably, described catalyst includes being coordinated rhodium catalyst and one or more in coordination platinum catalyst.
Described coordination rhodium catalyst includes but not limited to triphenylphosphine radium chloride.
Described coordination platinum catalyst includes but not limited to that methyl vinyl silicone coordination platinum, the platinum of oxolane coordination are urged
One or more in the platinum of agent and diethyl phthalate coordination.
Preferably, described coordination rhodium catalyst is (0.5～2) with the weight ratio of coordination platinum catalyst: 1.
Preferably, reaction temperature is 50 DEG C～70 DEG C.
The three of the purpose of the present invention are to overcome deficiency of the prior art, it is provided that a kind of amino-polyether block silicone oil
Preparation method.
For achieving the above object, the present invention is realized by techniques below means:
A kind of softening agent, it is characterised in that it includes amino-polyether block silicone oil prepared by aforesaid method.
Amino-polyether silicone oil in the present invention can be widely applied to coral fleece, pure wash, the fabric such as polyester-cotton blend, viscose rayon soft
Soft arrangement.
Amino-polyether silicone oil in the present invention is with 1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl two silica
The amino-polyether silicone oil of raw material production based on alkane, have of both advantage:
(1) fabric property:
Use the fabric that the amino-polyether silicone oil in the present invention processes, the fabric feeling processed than traditional silicone softening agent
More high resilience, softness, sliding glutinous, fluffy, plentiful, moist, soft, do not affect hydrophilic.Low-yellowing or non yellowing, be suitable for adding
White or light coloured fabrics, has low decolouring protective effect for dark fabric.
(2) in postfinishing process
1. can self emulsifying, it is not necessary to use emulsifying agent, therefore do not interfere with color fastness, be difficult to cause when soft finish and fade,
And not containing the restricted compounds such as APEO class, green safety is stable；
The most adsorbable formaldehyde, reduces content of formaldehyde on fabric, increases product environmental-protecting performance.
The most not floating oil, without silicon speckle, can redye, not glue cylinder, not roll banding.
4. working solution chemical stability is good, and high temperature resistant, acid and alkali-resistance (PH=3-12), resistance to high shear, with joining of other auxiliary agent
5 property are good, can be with yin, yang, nonionic textile auxiliary product with bathing use.
5. can use with fluorine system three-proof finishing agent and wrinkle resistant resin etc. simultaneously, do not interfere with and process fabric through fluorine-contained finishing agent
Three anti-effects.
6. can be used for padding, impregnating and spray processing (can be applicable to overflow machine system, dye bath produces with cylinder).
The preparation method of the amino-polyether silicone oil in the present invention: yield is up to 98%, the utilization of resources has reached to maximize；Nothing
The acidic materials such as sulphuric acid need to be used to make catalyst, without dangerous, production process safety；Production process will not produce solid waste.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail:
Comparative example
After 1,1,3,3-tetramethyl disiloxane and prestox ring tetrasilane (i.e. D4) are with concentrated sulphuric acid as catalyst reaction, warp
With generation end hydrogen modified silicon oil in sodium carbonate, end hydrogen modified silicon oil enters under chloroplatinic acid catalyst with allyl glycidyl ether again
Row additive reaction generates epoxy-capped polysiloxanes, and it is embedding that epoxy-capped polysiloxanes generates amino-polyether with amino-polyether reaction again
Section silicone oil.
In the present invention, the preparation method of amino-polyether silicone oil is:
Reacted by 1,1,3,3-tetramethyl disiloxane and allyl glycidyl ether and generate 1,3-diglycidyl ether oxygen
Base propyl group-1,1,3,3 tetramethyl disiloxane.1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane is again
Generating epoxy-capped polysiloxanes with prestox ring tetrasilane (i.e. D4), epoxy-capped polysiloxanes is raw with amino-polyether reaction again
Become amino polyether block silicone oil.
1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane by allyl glycidyl ether and 1,
1,3,3-tetramethyl disiloxane additive reaction gained, its production technology is:
A is 1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane.
B is allyl glycidyl ether.
C is 1,1,3,3-tetramethyl disiloxane.
D: for catalyst amount (unit is ppm).
Response time: unit is hour.
Temperature: DEG C.
Catalyst title in each embodiment and amount ratio
1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane in each embodiment and prestox ring
The weight ratio of tetrasilane is as shown in the table
E is epoxy-capped polysiloxanes,
I.e. CH2CH(O) CH2OC3H6Me2SiO(Me2SiO) nMe2SiC3H6OCH2(O) CHCH2.Epoxy-capped polysiloxanes rubs
You are molecular weight: 2000-20000.
A is 1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane.
F is prestox ring tetrasilane.
Epoxy-capped polysiloxanes in each embodiment with the amount ratio of amino-polyether is:
G is amino-polyether silicone oil.
Amino-polyether block silicone oil structural formula is:
Described a is in the range of (0～20)；B is in the range of (0～25)；N is in the range of (0～200)；In polyether block 60%
It is more than
E is epoxy-capped polysiloxanes,
I.e. CH2CH(O) CH2OC3H6Me2SiO(Me2SiO) nMe2SiC3H6OCH2(O) CHCH2.Epoxy-capped polysiloxanes rubs
You are molecular weight: 2000-20000.
H is amino-polyether.The molecular weight of described amino-polyether is 100～3000.Embodiment 1-3 amino-polyether is selected from
The ED-600 of Huntsman company；Embodiment 4-7 amino-polyether is selected from the ED-900 of Huntsman company；Embodiment 8-10 amino
Polyethers is selected from the ED-2003 of Huntsman company.
Epoxy-capped polysiloxanes is 60:40～95:5 with the weight ratio of amino-polyether.
Contrast experiment
Select the amino that amido silicon oil, the amino-polyether block silicone oil of comparative example 1 production and present invention process produce
Polyether block silicone oil carries out softening agent assessment of performance to coral fleece, the pure fabric such as cloth, polyester-mixed cotton cloth of washing, the softening agent of final preparation
Ammonia equivalent is 800-1600, contrasts in the case of comparative example is identical with the amino-polyether silicone oil ammonia equivalent that the present invention produces,
Experimental comparison's data see table:
In experiment,
Flexibility, flatness, fluffy sense: untrimmed cloth-like hand rank is set to 1 grade, flexibility from worst to
Optimal sorting is 5 grades, the expert of 10 evaluation flexibilities evaluate respectively, and comprehensive average level is final conclusion.
Xanthochromia degree: using SBDY-1 digital display whiteness instrument detection whiteness, the least whiteness of numerical value is the best, and the biggest whiteness of data is more
Low.
Alkali stability: the softening agent solution 50ml of configuration 20g/l, with NaOH solution adjust pH value be respectively 4,6,8,9,
10、12.The softening agent solution mixing up pH value being placed on magnetic force heating stirrer, warming while stirring, recording solution is muddy, drift
Temperature when wadding and floating oil.Occurring that the temperature of muddy, drift wadding and floating oil is the highest, stability is the best.
Heatproof stability: by the consumption of 100g/L, softening agent is made into working solution, is the condition of 100r/min in shearing force
Under, after stirring 2h under test different temperatures, there is the situation of oil droplet in chamber wall and working solution surface, occur that the temperature of oil droplet is the highest,
Heatproof stability is the best.
Embodiment in the present invention is only used for that the present invention will be described, is not intended that the restriction to right,
Those skilled in that art it is contemplated that other replacements being substantially equal to, all in scope.
Claims (3)
1. the preparation method of an amino-polyether block silicone oil, it is characterised in that comprise the steps:
1), allyl glycidyl ether is total at coordination rhodium catalyst and coordination platinum catalyst with 1,1,3,3-tetramethyl disiloxane
Reaction preparation 1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane under same-action；Described coordination rhodium catalysis
Agent is triphenylphosphine radium chloride；Described coordination platinum catalyst is that methyl vinyl silicone is coordinated platinum；Described coordination rhodium catalyst
It is (0.5-2) with the weight ratio of coordination platinum catalyst: 1；
2), 1,3-diglycidyl ether epoxide propyl group-1,1,3,3 tetramethyl disiloxane and the reaction of prestox ring tetrasilane obtain
Epoxy-capped polysiloxanes；The structural formula of epoxy-capped polysiloxanes is:
CH2CH(O)CH2OC3H6Me2SiO(Me2SiO)nMe2SiC3H6OCH2(O)CHCH2；Mole is 2000-20000；
3), epoxy-capped polysiloxanes reacts acquisition amino-polyether block silicone oil, described amino-polyether molecular weight with amino-polyether
For 100-3000, described amino-polyether block silicone oil structural formula is:
The preparation method of amino-polyether block silicone oil the most according to claim 1, it is characterised in that allyl glycidol
Ether is 50 DEG C-70 DEG C with the temperature of 1,1,3,3-tetramethyl disiloxane additive reaction.
3. the preparation method of a softening agent, it is characterised in that include step: 1), according to the method described in claim 1 or 2
Preparation includes amino-polyether block silicone oil；2), step 1 is re-used) the amino-polyether block silicone oil prepared prepares softening agent.
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| CN103351469B (en) * | 2013-05-31 | 2015-10-07 | 浙江安诺其助剂有限公司 | A kind of preparation method of block silicone oil softening agent |
| CN103483593B (en) * | 2013-09-23 | 2015-08-19 | 上海硅普化学品有限公司 | Amino-polyether and preparation method thereof, amino-polyether block silicone oil and preparation method thereof |
| CN103726338B (en) * | 2013-12-17 | 2015-11-25 | 薛成强 | A kind of manufacture method of non yellowing raising agent |
| CN103937257B (en) * | 2014-03-24 | 2017-01-25 | 惠州市安品新材料有限公司 | Organic silicone thixotropic agent and thixotropy addition type liquid silicone rubber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5484950A (en) * | 1992-12-21 | 1996-01-16 | Polyset Company, Inc. | Process for selective monoaddition to silanes containing two silicon-hydrogen bonds and products thereof |
| US20030020049A1 (en) * | 2001-07-30 | 2003-01-30 | Payne Donald N. | Modified silicon-based UV absorbers useful in crosslinkable polysiloxane coatings via sol-gel polymerization |
| CN102219905A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院化学研究所 | Organic silicon episulfide resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE297958T1 (en) * | 1996-03-04 | 2005-07-15 | Gen Electric | BLOCK COPOLYMERS BASED ON SILICONES AND AMINO POLYALKYLENE OXIDES |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5484950A (en) * | 1992-12-21 | 1996-01-16 | Polyset Company, Inc. | Process for selective monoaddition to silanes containing two silicon-hydrogen bonds and products thereof |
| US20030020049A1 (en) * | 2001-07-30 | 2003-01-30 | Payne Donald N. | Modified silicon-based UV absorbers useful in crosslinkable polysiloxane coatings via sol-gel polymerization |
| CN102219905A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院化学研究所 | Organic silicon episulfide resin and preparation method thereof |
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