CN109942823A - With the polyether silicones copolymer and synthetic method of good emulsifiability and application - Google Patents

With the polyether silicones copolymer and synthetic method of good emulsifiability and application Download PDF

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Publication number
CN109942823A
CN109942823A CN201711396288.9A CN201711396288A CN109942823A CN 109942823 A CN109942823 A CN 109942823A CN 201711396288 A CN201711396288 A CN 201711396288A CN 109942823 A CN109942823 A CN 109942823A
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polyether
catalyst
polyether silicones
silicones copolymer
synthetic method
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唐雄峰
黄登登
孙宇
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JIANGSU MAYSTA CHEMICAL CO Ltd
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JIANGSU MAYSTA CHEMICAL CO Ltd
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Abstract

The present invention relates to polyether silicones synthesis technical fields, especially a kind of to have following structure with the polyether silicones copolymer and synthetic method of good emulsifiability and application,Wherein: m value is 10-70;N value is 1-10;Q value is 0-4;R1、R2And R5For methyl or-CH2CH2CH2O(CH2CH2O)x(CH2CHCH3O)yR6, and R1、R2And R5It is identical or different, and R1、R2And R5It is not simultaneously methyl;X value is 10-70;Y value is 0-30;R3And R4For methyl or phenyl, and R3And R4It is identical or different;R6The alkyl for being 1-4 for-OH or carbon atom number.Compared with common polyether Organosiliconcopolymere, synthesizing polyether Organosiliconcopolymere of the present invention has more preferable emulsifiability.

Description

With the polyether silicones copolymer and synthetic method of good emulsifiability and application
Technical field
The present invention relates to polyether silicones synthesis technical field, specially a kind of polyethers with good emulsifiability is organic Siliceous copolymer and synthetic method and application.
Background technique
Polyurethane foam plastics is a kind of important synthetic material, and with porosity, relative density is small, specific strength is high, excellent Good physical mechanical property, acoustical behavior, electric property and chemical-resistance.According to the change of raw materials used difference and formula Change, polyurethane foam plastics can be made into soft, semi-rigid and rigid polyurethane foam.Polyurethane foam plastics is by a variety of originals Material is chemically reacted in a short time (such as isocyanates, polyalcohol, foaming agent etc.), and colloid is become by liquid and is become again High polymer experiencings the complex processes such as foaming, gel therebetween.
It in entire chemical reaction process, is acted on by polyurethane foam stabilizer, just uniform in foaming, foam can be made steady It is fixed, the foams of uniform foam cell are made.Its role mainly has:
(1) each component in emulsion foam system.The intermiscibility of each component in foam formulation is poor, foam stabiliser tool There is the molecular structure of amphipathic (oleophylic/hydrophilic), it can be made to be uniformly mixed with emulsion foam raw material, before improvement material reaction, instead Compatible state in answering, so that foamable reaction and cross-linking reaction be made to go on smoothly.
(2) nucleation and stable foam.Since foam stabiliser can reduce the surface tension of material, when stirring, is easy to make to mix The air entered forms nuclei of bubbles, these nuclei of bubbles play the role of similar " nucleus ", and the gas for reacting generation enters nuclei of bubbles simultaneously Bubble is set constantly to grow up;In foaming process, foam stabiliser makes the cell wall of thinning by reducing the stress in cell wall Stablize, being uniformly distributed makes fizzy, collapse hole without causing foam aperture to merge with macropore.
(3) closed pore/aperture effect.It is good exhausted that rigid polyurethane foam abscess closed pore can just be such that foamed product has Thermal effect and enough mechanical strengths, foam stabiliser obtain uniform foam cell by the way that the surface tension of foaming system is effectively reduced Fine and closely woven and rate of closed hole is higher than 95% foams, to guarantee foam thermal insulation performance.The abscess of flexible polyurethane foam is necessary It is aperture can just make product soft and springiness.Due to the effect of foam stabiliser, when system is in the low viscosity stage, Cell wall is stablized, and when air bubble growth is to the thickness for being suitable for aperture, the abscess under the collective effect of catalyst and foam stabilizer Rupture is " aperture ".The defects of foam stabiliser can be by controlling the foamed open cell time, eliminating foam cracking, closed pore, assigns The good air penetrability of foam and comfort property.Therefore foam stabiliser not only plays even bubble, and to the bubble of polyurethane foam The properties of product such as pore structure, intensity, thermal coefficient, air penetrability have an important influence, and play irreplaceable role.
For polyurethane foam stabilizer mainly using siloxanes segment as hydrophobic group, polyether segment is that hydrophilic group passes through chemical bond Be formed by connecting polyether silicones copolymer.
Patent CN1644598A discloses a kind of polyether silicones copolymer as polyurethane foam stabilizer and prepares hard poly- Urethane foam.
Patent CN101125952A discloses one kind with organic silicon polyether copolymer and preparation method thereof, as polyurethane foam Stabilizer can be widely used for the polyurethane foam technique of pentane-blown system.
Patent CN102504263A discloses a kind of polyurethane foam stabilizer for having good nucleation performance, can be significant Reduce foaming system surface tension.
Patent CN102604107A discloses a kind of polyurethane foam for hard polyaminoester or polyisocyanurate foam Stabilizer, polyethers end are secondary or tert-hydroxyl.
Patent CN102604106A discloses a kind of polyurethane foam for hard polyaminoester or polyisocyanurate foam Stabilizer, polyether moiety sealing end.
Patent CN105873994A is disclosed the composition suitable for preparing hard polyaminoester or polyisocyanurate foam Comprising at least two different type organic silicon polyether copolymers as foam stabiliser.
The polyether silicones copolymer of above-mentioned Patent design synthesis is mainly used for rigid polyurethane foam as foam stabiliser Foam provides good mobile performance, surface property and low thermal conductivity for it.The present invention is then to synthesize one kind for hard polyurethane The organic silicon polyether copolymer of ester foam stabiliser shows preferably to emulsify than the organic silicon polyether copolymer of similar structures Property.
Summary of the invention
The purpose of the present invention is to provide a kind of polyether silicones copolymers and synthetic method with good emulsifiability And application, to solve the problems, such as that organic silicon polyether copolymer emulsifying effectiveness is bad in the prior art.
To achieve the above object, the invention provides the following technical scheme:
A kind of polyether silicones copolymer with good emulsifiability, has following structure,
Wherein:
M value is 10-70;N value is 1-10;Q value is 0-4;
R1、R2And R5For methyl or-CH2CH2CH2O(CH2CH2O)x(CH2CHCH3O)yR6, and R1、R2And R5It is identical or not Together, and R1、R2And R5It is not simultaneously methyl;
X value is 10-70;Y value is 0-30;
R3And R4For methyl or phenyl, and R3And R4It is identical or different;
R6The alkyl for being 1-4 for-OH or carbon atom number.
The synthetic method of polyether silicones copolymer of the present invention, comprising the following steps:
(1) using allyl alcohol as initiator, ethylene oxide and propylene oxide are added in the reactor, in the presence of a catalyst, Pressure is controlled in≤0.4MPa, and 4-6h is reacted under the conditions of 100-130 DEG C, obtains allyl polyether;
(2) allyl polyether blocks: according to a kind of Chinese patent CN102492130A " envelope of base catalysis one-step method preparation Method described in end polyethers and preparation method thereof " is implemented.
(3) with octamethylcy-clotetrasiloxane, two silicon of octamethylcy-clotetrasiloxane, tetramethyldihydrogendisiloxane and hexamethyl Oxygen alkane under the action of catalyst, reacts 3-7h under the conditions of reaction temperature is 25-90 DEG C, obtains hydrogen containing siloxane for raw material;
(4) hydrogen containing siloxane, allyl polyether, platinum catalyst are added in reactor, and normal pressure is warming up to 80-130 DEG C instead 1-10h is answered, polyether silicones copolymer is obtained.
The synthetic method of polyether silicones copolymer of the present invention, wherein catalyst described in step (1) is alkali Property catalyst, dosage be ethylene oxide and propylene oxide gross mass 0.1-0.5%.
The synthetic method of polyether silicones copolymer of the present invention, wherein catalyst described in step (1) is preferred For KOH or NaOH.
The synthetic method of polyether silicones copolymer of the present invention, wherein catalyst described in step (3) is acidity Any one in carclazyte, sulfuric acid and trifluoromethanesulfonic acid or combination;Its dosage is the 1- of the raw materials used gross mass of the step 4%.
The synthetic method of polyether silicones copolymer of the present invention, wherein catalyst described in step (3) is preferably Sulfuric acid.
The synthetic method of polyether silicones copolymer of the present invention, wherein used catalyst is urged in step (4) for platinum Agent, dosage are the 3-30ppm of the step total mass of raw material.
Application of the polyether silicones copolymer of the present invention in production polyurethane foam.
Preferably, the polyurethane foam is hard polyurethane foams;It counts, gathers according to the polyalcohol pphp of 100 mass parts The mass fraction of ether Organosiliconcopolymere is 1-5pphp.
Further, it is counted according to the polyalcohol pphp of 100 mass parts, the mass fraction of polyether silicones copolymer is 2- 3pphp。
Compared with prior art, the beneficial effects of the present invention are: the present invention utilizes hydrogen containing siloxane and allyl polyether Synthesizing polyether Organosiliconcopolymere is designed by hydrosilylation.Compared with common polyether Organosiliconcopolymere, the present invention is closed There is more preferable emulsifiability at polyether silicones copolymer.
Detailed description of the invention
Fig. 1 is polyether silicones copolymer emulsifying capacity test result photo.
Fig. 2 is product AK8830, AK8872 emulsifying capacity test result photo.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation method of the polyether silicones copolymer with good emulsifiability:
(1) allyl alcohol 23.3g, ethylene oxide 176.7g are added in the reactor, in the presence of 0.80gKOH catalyst, pressure Power≤0.4MPa, reaction temperature react 5h under the conditions of being 120 DEG C, obtain allyl polyether (I);
(2) by octamethylcy-clotetrasiloxane 107.8g, tetramethyl-ring tetrasiloxane 29.2g, tetramethyldihydrogendisiloxane 13.0g, in 25 DEG C of reaction 6h, neutralizes filtering, obtains hydrogen containing siloxane (I) under effect of sulfuric acid.
(3) reactor is added in hydrogen containing siloxane (I) 48.1g, allyl polyether (I) 151.9g, in 6ppm platinum catalyst Under co-catalyst effect, it is heated to 90-120 DEG C of reaction 3h under nitrogen protection under normal pressure, obtains polyether silicones copolymer (I), structure are as follows: R-Si (CH3)2-O-[Si(CH3)2]15-O-[Si(CH3)R]5-O-(CH3)2SiR, wherein R=-CH2CH2CH2 (OCH2CH2)10OH。
Embodiment 2
A kind of preparation method of the polyether silicones copolymer with good emulsifiability:
(1) allyl alcohol 13.9g, ethylene oxide 158.3g, propylene oxide 27.8g, in 0.70gKOH are added in the reactor In the presence of catalyst, pressure≤0.4MPa, reaction temperature be 120 DEG C under the conditions of react 5h, obtain allyl polyether (II);
(2) by octamethylcy-clotetrasiloxane 128.6g, tetramethyl-ring tetrasiloxane 15.6g, tetramethyldihydrogendisiloxane 5.8g, in 25 DEG C of reaction 6h, neutralizes filtering, obtains hydrogen containing siloxane (I) under effect of sulfuric acid.
(3) reactor is added in hydrogen containing siloxane (II) 53.3g, allyl polyether (II) 146.7g, in 8ppm platinum catalysis Under agent and co-catalyst effect, it is heated to 90-120 DEG C of reaction 4h under nitrogen protection under normal pressure, obtains polyether silicones copolymerization Object (I), structure: R-Si (CH3)2-O-[Si(CH3)2]40-O-[Si(CH3)R]6-O-(CH3)2SiR, wherein R=-CH2CH2CH2 (OCH2CH2)15(OCH2CHCH3)2OH。
Embodiment 3
(1) allyl alcohol 9.0g, ethylene oxide 82.4g, propylene oxide 108.6g, in 0.70g KOH are added in the reactor In the presence of catalyst, pressure≤0.4MPa, reaction temperature be 120 DEG C under the conditions of react 5h, obtain allyl polyether (III);
(2) allyl polyether (III) carries out methyl blocking according to patent CN102492130A the method, obtains methyl envelope Allyl-terminated polyether (III).
(3) by octamethylcy-clotetrasiloxane 139.9g, tetramethyldihydrogendisiloxane 10.1g under effect of sulfuric acid in 25 DEG C 6h is reacted, filtering is neutralized, obtains hydrogen containing siloxane (III).
(4) reactor is added in hydrogen containing siloxane (III) 74.1g, methyl blocking allyl polyether (III) 125.9g, Under 6ppm platinum catalyst and co-catalyst effect, it is heated to 90-120 DEG C of reaction 3h under nitrogen protection under normal pressure, obtains polyethers Organosiliconcopolymere (III), structure: R-Si (CH3)2-O-[Si(CH3)2]25-O-(CH3)2SiR, wherein R=-CH2CH2CH2 (OCH2CH2)12(OCH2CHCH3)12OCH3
Embodiment 4
(1) allyl alcohol 3.0g, ethylene oxide 142.5g, propylene oxide 54.5g, in 1.00g KOH are added in the reactor In the presence of catalyst, pressure≤0.4MPa, reaction temperature be 120 DEG C under the conditions of react 5h, obtain allyl polyether (IV);
(2) by octamethylcy-clotetrasiloxane 131.8g, tetramethyl-ring tetrasiloxane 14.3g, tetramethyldihydrogendisiloxane 4.0g, in 25 DEG C of reaction 6h, neutralizes filtering, obtains hydrogen containing siloxane (IV) under effect of sulfuric acid.
(3) reactor is added in hydrogen containing siloxane (IV) 17.2g, allyl polyether (IV) 182.8g, in 10ppm platinum catalysis Under agent and co-catalyst effect, it is heated to 90-120 DEG C of reaction 4h under nitrogen protection under normal pressure, obtains polyether silicones copolymerization Object (IV), structure: R-Si (CH3)2-O-[Si(CH3)2]60-O-[Si(CH3)R]8-O-(CH3)2SiR, wherein R=-CH2CH2CH2 (OCH2CH2)62(OCH2CHCH3)18OH。
Embodiment 5
(1) by octamethylcy-clotetrasiloxane 133.5g, tetramethyl-ring tetrasiloxane 12.4g, hexamethyldisiloxane 4.2g In 50 DEG C of reaction 5h under Emathlite effect, filtering obtains hydrogen containing siloxane (V).
(2) reactor is added in hydrogen containing siloxane (V) 57.3g, allyl polyether (III) 142.8g, in 10ppm platinum catalysis Under agent and co-catalyst effect, it is heated to 90-120 DEG C of reaction 4h under nitrogen protection under normal pressure, obtains polyether silicones copolymerization Object (V), structure: Si (CH3)3-O-[Si(CH3)2]70-O-[Si(CH3)R]8-O-Si(CH3)3, wherein R=-CH2CH2CH2 (OCH2CH2)12(OCH2CHCH3)12OCH3
Embodiment 6
Emulsifiability test:
(1) polyether silicones copolymer made from embodiment 1-2 is applied to formula A:
Table 1
(2) polyether silicones copolymer made from embodiment 3-5 is applied to formula B:
Table 2
Each component is uniformly mixed in proportion, observation is stood, as shown in Fig. 1 and table 3.
Table 3
The above result shows that: using polyether silicones copolymer prepared by the present invention production polyurethane foam polyethers/ Polyester polyol system all has good emulsifying capacity.
(it is limited that share is learned in Dehua Mei Si, Jiangsu by polyether silicones copolymer product AK8830, AK8872 in the prior art Company, polyurethane foam stabilizer) for being formulated A and being formulated the emulsifiability of B as shown in Fig. 2 and table 4.
Table 4
Polyurethane foam stabilizer Pentamethylene It is formulated A
AK8830 10-20 parts 6h layering
AK8872 10-20 parts 6h layering
Polyurethane foam stabilizer Pentamethylene It is formulated B
AK8830 8-13 parts 2h layering
AK8872 8-13 parts 2h layering
Compared to common polyether Organosiliconcopolymere product (AK8830, AK8872), synthesizing polyether organosilicon of the present invention is total Polymers has more preferable emulsifiability.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (10)

1. a kind of polyether silicones copolymer with good emulsifiability, it is characterised in that: it has following structure,
Wherein:
M value is 10-70;N value is 1-10;Q value is 0-4;
R1、R2And R5For methyl or-CH2CH2CH2O(CH2CH2O)x(CH2CHCH3O)yR6, and R1、R2And R5It is identical or different, and R1、R2And R5It is not simultaneously methyl;
X value is 10-70;Y value is 0-30;
R3And R4For methyl or phenyl, and R3And R4It is identical or different;
R6The alkyl for being 1-4 for-OH or carbon atom number.
2. the synthetic method of polyether silicones copolymer described in claim 1, which comprises the following steps:
(1) using allyl alcohol as initiator, ethylene oxide and propylene oxide are added in the reactor, in the presence of a catalyst, pressure Control reacts 4-6h under the conditions of 100-130 DEG C, obtains allyl polyether in≤0.4MPa;
(2) allyl polyether blocks;
(3) with octamethylcy-clotetrasiloxane, octamethylcy-clotetrasiloxane, tetramethyldihydrogendisiloxane and hexamethyldisiloxane Under the action of catalyst for raw material, 3-7h is reacted under the conditions of reaction temperature is 25-90 DEG C, obtains hydrogen containing siloxane;
(4) hydrogen containing siloxane, allyl polyether, platinum catalyst are added in reactor, and normal pressure is warming up to 80-130 DEG C of reaction 1- 10h obtains polyether silicones copolymer.
3. the synthetic method of polyether silicones copolymer according to claim 2, it is characterised in that: described in step (1) Catalyst be basic catalyst, dosage be ethylene oxide and propylene oxide gross mass 0.1-0.5%.
4. the synthetic method of polyether silicones copolymer according to claim 3, it is characterised in that: described in step (1) Catalyst be KOH or NaOH.
5. the synthetic method of polyether silicones copolymer according to claim 2, it is characterised in that: described in step (3) Catalyst is any one or combination in Emathlite, sulfuric acid and trifluoromethanesulfonic acid;Its dosage is that the step is raw materials used The 1-4% of gross mass.
6. the synthetic method of polyether silicones copolymer according to claim 5, it is characterised in that: described in step (3) Catalyst is sulfuric acid.
7. the synthetic method of polyether silicones copolymer according to claim 2, it is characterised in that: described in step (4) Catalyst is platinum catalyst, and dosage is the 3-30ppm of the step total mass of raw material.
8. application of the polyether silicones copolymer described in claim 1 in production polyurethane foam.
9. the application of polyether silicones copolymer according to claim 8, it is characterised in that: the polyurethane foam is hard Matter polyurethane foam;It is counted according to the polyalcohol pphp of 100 mass parts, the mass fraction of polyether silicones copolymer is 1-5pphp.
10. the application of polyether silicones copolymer according to claim 9, it is characterised in that: according to the more of 100 mass parts First alcohol pphp meter, the mass fraction of polyether silicones copolymer are 2-3pphp.
CN201711396288.9A 2017-12-21 2017-12-21 With the polyether silicones copolymer and synthetic method of good emulsifiability and application Pending CN109942823A (en)

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CN111040176A (en) * 2019-12-27 2020-04-21 江苏美思德化学股份有限公司 Organic silicon polyether copolymer and preparation method and application thereof
CN111748099A (en) * 2020-07-08 2020-10-09 上海麦豪新材料科技有限公司 Preparation method of polyether organic silicon copolymer
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CN111013522A (en) * 2019-12-26 2020-04-17 江苏美思德化学股份有限公司 Alkyl polyether co-modified polysiloxane and continuous synthesis device and method thereof
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CN111040228A (en) * 2019-12-27 2020-04-21 江苏美思德化学股份有限公司 Surfactant, preparation method and application thereof, and polyurethane high-resilience foam
CN111040176A (en) * 2019-12-27 2020-04-21 江苏美思德化学股份有限公司 Organic silicon polyether copolymer and preparation method and application thereof
CN111748099A (en) * 2020-07-08 2020-10-09 上海麦豪新材料科技有限公司 Preparation method of polyether organic silicon copolymer
CN112724452A (en) * 2020-12-29 2021-04-30 南京美思德新材料有限公司 Surfactant, preparation method and application thereof
CN112724452B (en) * 2020-12-29 2022-12-16 南京美思德新材料有限公司 Surfactant, preparation method and application thereof

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Application publication date: 20190628