CN117659409A - Bio-based polyether modified polysiloxane, preparation method thereof, foam stabilizer and polyurethane foam - Google Patents
Bio-based polyether modified polysiloxane, preparation method thereof, foam stabilizer and polyurethane foam Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 15
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Abstract
The invention relates to the technical field of bio-based polyurethane, in particular to bio-based polyether modified polysiloxane, a preparation method thereof, a foam stabilizer and polyurethane foam. The structural formula of the bio-based polyether modified polysiloxane is shown as follows:wherein m=45-75, n=3-10; r1 and R3 each independently represent a bio-based group derived from a bio-based substance having a terminal double bond and not containing a hydroxyl group therein; r2 represents-CH 2 CH 2 CH 2 (OC 2 H 4 ) a (OC 3 H 6 ) b OR4, wherein a=10-30, b=10-30, R4 is H OR containsAlkyl of 1-4 carbons. The bio-based polyether modified polysiloxane can be used for preparing polyurethane foam, and the problem of mechanical property reduction caused by the partial substitution of petroleum-based polyol, such as the problem of improvement of tensile strength, tearing strength, indentation hardness and the like, can be solved.
Description
Technical Field
The invention relates to the technical field of bio-based polyurethane, in particular to bio-based polyether modified polysiloxane, a preparation method thereof, a foam stabilizer and polyurethane foam.
Background
Polyurethane (PU) materials can be widely used mainly because of the abundant raw material types, molecular chain structure, adjustable molecular weight, outstanding comprehensive performance and adaptability to different use requirements, and can be formed by almost all processing methods of high polymer materials. In the actual synthesis process, the PU chain structure and the molecular weight can be regulated and controlled by changing the types of isocyanate and polyol, the proportion of isocyanate groups to active hydrogen compounds or the addition amount of catalysts in the reaction process, the reaction process and other methods, so that the polyurethane material shows various performance characteristics.
Polyurethanes are still currently mainly obtained by polyaddition between isocyanates and polyols to obtain linear or crosslinked structures. The diversity of PU stems from the structural diversity of polyols and isocyanates and the special nature of the urethane groups. Polyurethane foams (PUFs) are mainly of two types: a flexible foam (F-PUF) with an open cell structure and a rigid foam (R-PUF) with a closed cell structure. Polyurethane soft foam is applied to the fields of automobiles, furniture, home furnishings and the like due to the characteristics of opening holes, rebound and the like, and is tightly contacted with a human body, so that the application of a biological base in the soft foam is of great concern.
The research on bio-based polyurethanes has focused mainly on polyurethane polyols. The properties of the polyol have a profound effect on the properties and structure of the final foam. Most researchers choose to use vegetable oil polyols instead of petroleum-based polyols because vegetable oils are mostly unsaturated fatty acids containing double bonds and ester groups that can be modified. The common vegetable oils include soybean oil, castor oil, cotton seed oil, palm oil, etc., and the synthetic methods of the vegetable oil polyol mainly comprise two methods of modifying double bond functional groups (an epoxidation ring-opening method, an ozone oxidation method, a hydroformylation method, etc.) and modifying ester functional groups (an ester exchange method, an ammonolysis method, etc.). In addition to the usual vegetable oil modified polyols, there are polylactide polyols, lignin polyols, cardanol polyols, and the like.
For example, CN201010178740.6 was modified with palm oil to prepare a soft foam polyether polyol. Compared with the prior polyether polyol, the bio-based polyether polyol prepared by the method has the characteristics of convenient raw material purchase, regeneration and production cost reduction, and can better meet the requirement of environmental protection. It is not enough that this process still requires the use of the technical raw materials Propylene Oxide (PO) and Ethylene Oxide (EO). For another example, CN202111586139.5 discloses a method for preparing polyurethane soft foam by using vegetable oil polyol, the prepared polyurethane soft foam has high bio-base content, can obviously reduce dependence on petrochemical products, and is environment-friendly. The performance of the prepared polyurethane foam is consistent with that of petroleum-based foam, but the operation process is more complex than that of the conventional polyurethane foam. CN202211359929.4 discloses a method for preparing polyurethane foam from castor oil polyol, and the prepared sponge has better mechanical properties, elastic comfort and bacteriostasis compared with the bio-based series in the market at present. The foam has the biggest characteristics that castor oil base containing a biological base structure is used, and has better environmental protection effect. Mark F. Et al (Mark F. Sonnenschein, benjamin L, et al Polymer,54 (2013) 2511-2520.) A series of polyurethane foams were produced by adding a designed soybean oil derived polyol (SBOP) to gradually reduce the petroleum-based polyether polyol content, and the deficiencies in the tensile and tear strength of the bio-based polyurethane foam could be ameliorated by designing the foam formulation.
In the process of applying the bio-based polyether to polyurethane foam instead of the conventional polyether polyol, researchers have also found some problems of the bio-based polyether, such as darkening of polyurethane foam, cracking of the foam, and degradation of mechanical properties. So that the bio-based polyether cannot be completely used for replacing petrochemical-based polyether at present, and can be only used in a mixed way or is called as partial replacement. Meanwhile, the prior literature and patents are also not substantially concerned with the impact of silicone surfactants on bio-based polyurethane foam products.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a bio-based polyether modified polysiloxane and a preparation method thereof, a foam stabilizer and polyurethane foam. The polyurethane foam prepared by the bio-based polyether modified polysiloxane can solve the problem of mechanical property reduction caused by the partial substitution of petroleum-based polyol by the bio-based polyol, such as the problem of improving tensile strength, tearing strength, indentation hardness and the like.
The invention is realized in the following way:
in a first aspect, the present invention provides a bio-based polyether modified polysiloxane having the structural formula:
wherein m=45-75, n=3-10;
r1 and R3 each independently represent a bio-based group derived from a bio-based substance having a terminal double bond and containing no hydroxyl group therein;
r2 represents-CH 2 CH 2 CH 2 (OC 2 H 4 ) a (OC 3 H 6 ) b OR4, wherein a=10-30, b=10-30,
r4 is H or alkyl containing 1-4 carbon atoms.
In alternative embodiments, the biobased material is selected from the group consisting of rosin esters or alkenyl-containing monoterpenes;
preferably, the rosin allyl ester compound is selected from at least one of rosin allyl ester, hydrogenated rosin allyl ester, rosin allyl methyl ester, hydrogenated rosin allyl methyl ester, rosin allyl ethyl ester and hydrogenated rosin allyl ethyl ester;
preferably, the alkenyl-containing monoterpene compound comprises an alkenyl-containing monocyclic monoterpene compound; more preferably limonene;
more preferably, the bio-based groups are grafted to the siloxane backbone by hydrosilylation.
In a second aspect, the present invention provides a method for preparing the bio-based polyether modified polysiloxane according to the previous embodiment, comprising: reacting the terminal hydrogen-containing polysiloxane with a bio-based substance under the action of a catalyst to form polysiloxane with a terminal group containing a bio-base;
then, the polysiloxane with the end group containing the biological group and tetramethyl tetrahydrocyclotetrasiloxane are subjected to acid catalysis to form low hydrogen polysiloxane containing the biological group;
the biobased low hydrogen containing polysiloxane and the terminal allyl polyether are then mixed to react to form the biobased polyether modified polysiloxane.
In an alternative embodiment, the step of forming the end group bio-based containing polysiloxane comprises: mixing the hydrogen-containing polysiloxane, the bio-based material and the catalyst, and reacting for 2-6 hours at 80-100 ℃;
preferably, the mass percent of the hydrogen-containing polysiloxane at the end and the bio-based substance is 11-7:89-93;
preferably, the catalyst is selected from complexes containing at least one of palladium, rhodium and platinum; preferably chloroplatinic acid;
preferably, the catalyst is used in an amount of 5 to 10ppm.
In an alternative embodiment, the step of forming the biobased low hydrogen containing polysiloxane comprises: mixing polysiloxane with the end group containing biological groups, tetramethyl tetrahydrocyclotetrasiloxane and an acid catalyst, and reacting for 2-6 hours at 40-80 ℃;
preferably, the mass percentage ratio of the end group containing bio-based polysiloxane to the tetramethyl-tetrahydrocyclotetrasiloxane is 92-96:8-4;
preferably, the acid catalyst is selected from at least one of acid clay, sulfuric acid, and trifluoro-benzenesulfonic acid;
preferably, the acid catalyst is used in an amount of 0.1 to 1.5% of the total amount of raw materials forming the bio-based low hydrogen containing polysiloxane.
In an alternative embodiment, the step of forming the bio-based polyether modified polysiloxane comprises: mixing the low-hydrogen polysiloxane containing biological base, terminal allyl polyether, amine auxiliary agent and catalyst, and reacting for 2-6 hours at 80-100 ℃;
preferably, the mass percent ratio of the terminal allyl polyether to the biobased low hydrogen-containing polysiloxane is 80-70:20-30;
preferably, the catalyst is selected from complexes containing at least one of palladium, rhodium and platinum; preferably chloroplatinic acid;
preferably, the catalyst is used in an amount of 5 to 10ppm;
preferably, the amine auxiliary agent is selected from at least one of N, N-dimethylethanolamine, N-dibutylethanolamine, 3-dimethylpropylamine and 2-butylaminoethanol;
preferably, the amine adjuvant is used in an amount of 50-500ppm.
In an alternative embodiment, the step of forming the hydrogen-terminated polysiloxane comprises: mixing octamethyl cyclotetrasiloxane, 1, 3-tetramethyl disiloxane and an acid catalyst, and reacting for 2-6 hours at 40-80 ℃;
preferably, the mass percent ratio of the octamethyl cyclotetrasiloxane and the 1, 3-tetramethyl disiloxane is 2-4:98-96;
preferably, the acid catalyst is selected from at least one of acid clay, sulfuric acid, and trifluoro-benzenesulfonic acid;
preferably, the acid catalyst is used in an amount of 0.1 to 1.5% of the total amount of raw materials forming the hydrogen-terminated polysiloxane.
In a third aspect, the present invention provides a foam stabilizer, the raw materials of which comprise the bio-based-containing polyether modified polysiloxane of the previous embodiments.
In a fourth aspect, the present invention provides a polyurethane foam, the starting material of which comprises a polyol, the bio-based polyether modified polysiloxane of the previous embodiment, or the foam stabilizer of the previous embodiment.
In an alternative embodiment, the polyurethane foam is a flexible polyurethane foam;
preferably, the mass percent ratio of the polyol to the bio-based polyether modified polysiloxane is 40:1.0-1.1;
preferably, the hydroxyl number of the polyol is from 30 to 80mgKOH/g, preferably from 45 to 65mgKOH/g.
The invention has the following beneficial effects: the bio-based polyether modified polysiloxane formed by grafting the bio-based groups at the two ends of the main chain of the polysiloxane can obviously improve the problem of mechanical property reduction caused by the partial substitution of petroleum-based polyol by the bio-based polyol, such as the improvement of high tensile strength, tearing strength, indentation hardness and the like. Specifically, the bio-based polyether modified polysiloxane is used as a foam stabilizer, and the bio-based polyol and petrochemical polyol in the bio-based polyurethane foam can have better compatibility and dispersibility by the bio-based groups at two ends of the main chain of the bio-based polyether modified polysiloxane, so that the reaction is more sufficient, and the problem of the reduction of the mechanical property of the bio-based polyurethane flexible foam is solved. In addition, compared with the bio-based content of the common bio-based grafted modified polysiloxane, the bio-based content of the bio-based-containing polyether modified polysiloxane provided by the embodiment of the invention is obviously improved, so that the use of petrochemical base materials is reduced, the carbon emission is reduced, and the environment is protected and the resource is saved.
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 embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the present invention provides a bio-based polyether modified polysiloxane having the structural formula:
wherein m=45-75, n=3-10;
r1 and R3 each independently represent a bio-based group derived from a bio-based substance having a terminal double bond and containing no hydroxyl group therein;
r2 represents-CH 2 CH 2 CH 2 (OC 2 H 4 ) a (OC 3 H 6 ) b OR4, wherein a＝10-30，b＝10-30，
R4 is H or alkyl containing 1-4 carbon atoms.
Specifically, the bio-based group is a bio-based material grafted onto the polysiloxane backbone by hydrosilylation, wherein the bio-based material may be selected from the group consisting of rosin allyl esters, such as rosin allyl estersHydrogenated allyl rosin ester->Any one or two or more of rosin methyl ester, hydrogenated rosin methyl ester, rosin ethyl ester and hydrogenated rosin ethyl ester.
The biobased material may also be an alkenyl-containing monoterpene; for example, alkenyl-containing monocyclic monoterpenes; more preferably limonene
It should be noted that the above bio-based materials are merely examples of embodiments of the present invention, and other bio-based materials having terminal double bonds and not containing hydroxyl groups in the prior art are within the scope of the embodiments of the present invention as long as they can be grafted onto the polysiloxane backbone.
In a second aspect, the present invention provides a method for preparing the bio-based polyether modified polysiloxane according to the previous embodiment, comprising:
s1, forming terminal hydrogen-containing polysiloxane:
octamethyl cyclotetrasiloxane (D4) and 1, 3-tetramethyl disiloxane (TS) are used as raw materials, acid catalysis is carried out at 40-80 ℃ for 2-6h, and the end hydrogen-containing polysiloxane is prepared after post-treatment. Wherein, D4:TS=2-4:98-96 (wt%, the mass percentage ratio of the raw materials is the same as that described in the examples of the invention). The acid catalyst comprises acid clay, sulfuric acid, trifluoro benzene sulfonic acid and the like, and the dosage of the acid catalyst is 0.1-1.5% of the total amount of raw materials for forming hydrogen-containing polysiloxane at the end.
S2, forming polysiloxane with a terminal group containing a biological group;
taking the hydrogen-containing polysiloxane at the end, which is obtained in the step S1, and the bio-based substance which contains terminal double bonds and does not contain hydroxyl groups as raw materials, adding a catalyst at 80-100 ℃, preserving heat for 2-6h, and performing post-treatment to obtain the polysiloxane with the bio-based at the end group.
Among these biobased materials include, but are not limited to, allyl rosin esters, allyl hydrogenated rosin esters, limonene, and the like. Terminal hydrogen-containing polysiloxane: biobased material = 11-7:89-93. The catalyst is a complex containing one or more than 2 of palladium, rhodium and platinum, preferably chloroplatinic acid, and the dosage is 5-10ppm.
S3, forming low-hydrogen polysiloxane containing biological groups;
taking polysiloxane (BBS for short) with a biological group at the end group formed by S2 and tetramethyl tetrahydrocyciotetrasiloxane (D4H for short) as raw materials, carrying out acid catalysis at 40-80 ℃ for 2-6H, and carrying out post-treatment to obtain the low-hydrogen polysiloxane with the biological group. BBS d4h=92-96:8-4; the acid catalyst comprises any one or more than 2 of acid clay, sulfuric acid, trifluoro-benzene sulfonic acid and the like, and the dosage of the acid catalyst is 0.1-1.5% of the total amount of raw materials for forming the bio-based low-hydrogen polysiloxane.
S4, forming bio-based polyether modified polysiloxane;
adding allyl-terminated polyether, low-hydrogen polysiloxane containing biological groups, amine auxiliary agents and the like into a reaction kettle, heating to 80-100 ℃ in a dry nitrogen atmosphere, adding a catalyst, and reacting for 2-6h under normal pressure to obtain the polyether modified polysiloxane containing biological groups.
Wherein, end allyl polyether: biobased low hydrogen polysiloxane = 80-70%:20-30%; the catalyst is a complex containing one or more than 2 of palladium, rhodium or platinum, preferably chloroplatinic acid, and the dosage is 5-10ppm. The amine promoter is one or more of N, N-dimethylethanolamine, N-dibutylethanolamine, 3-dimethylpropylamine and 2-butylaminoethanol, and the dosage is 50-500ppm.
The terminal allyl polyether used in this step is an existing commercially available polyether.
In a third aspect, the present invention provides a foam stabilizer, the raw materials of which comprise the bio-based-containing polyether modified polysiloxane of the previous embodiments.
In a fourth aspect, the present invention provides a polyurethane foam, the starting material of which comprises a polyol, the bio-based polyether modified polysiloxane of the previous embodiment, or the foam stabilizer of the previous embodiment.
Wherein the hydroxyl value of the polyol is 30 to 80mgKOH/g, preferably 45 to 65mgKOH/g. Such as polyether diols, polyether triols, polyester diols, polyester triols, and hydroxyl terminated polyolefin polyols. Optionally bio-based polyols such as castor oil polyol and soybean oil polyol
The polyurethane foam is soft polyurethane foam, and the mass percentage ratio of the polyol to the bio-based polyether modified polysiloxane is 40:1.0-1.1.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment of the invention provides a preparation method of bio-based polyether modified polysiloxane, which comprises the following steps:
into a 500ml three-necked flask equipped with a mechanical stirrer, 9.0g of 1, 3-tetramethyldisiloxane and 298.2g of octamethyl cyclotetrasiloxane were charged, 0.3g of trifluoromethanesulfonic acid was added, and the mixture was stirred at 60 to 65℃for 3 hours, followed by post-treatment to give an average structure of M H D 60 M H Hydrogen terminated polysiloxanes of (2). Wherein M is H Is (CH) 3 ) 2 HSiO-, D is-Si (CH) 3 ) 2 O-。
39.0g of allyl rosin ester and 261.0g of hydrogen terminated polysiloxane M H D 60 M H The mixture was mixed, heated to 85 to 90℃and stirred for 10 minutes, and 10ppm of Pt (chloroplatinic acid in ethanol) was added. Maintaining the mixture in the bottle at 85-90 ℃ for reaction for 5h, and obtaining yellow transparent viscous liquid after treatment, wherein the average structural formula of the viscous product is M 1 D 60 M 1 I.e., allyl rosin ester terminated polysiloxanes. Wherein the method comprises the steps of
283.8g of allyl rosin ester terminated polysiloxane M 1 D 60 M 1 Mixing with 16.2g tetramethyl tetra-four-hydrogen cyclosiloxane, adding 0.3g trifluoro-benzene sulfonic acid, stirring at 60-65 deg.C for 5h, post-treating to obtain the final product with average structure M 1 D 60 D H 5 M 1 Allyl rosin ester terminated low hydrogen containing polysiloxanes. Wherein D is H is-Si (CH) 3 )HO-。
85.4g of the average structure M 1 D 60 D H 5 M 1 107.3g of allyl-initiated, methyl-terminated polyether A (having an average molecular weight of 3000 and containing 40% by weight of glycidol groups and 60% by weight of glycidol groups) (available from Zhejiang Royal technology Co., ltd.) and 107.3g of allyl-initiated, methyl-terminated polyether B (having an average molecular weight of 1500 and containing 40% by weight of oxirane groups and 60% by weight of glycidol groups) (available from Zhejiang Royal technology Co., ltd.) were mixed, 200ppm of N, N-dibutylethanolamine was added and stirred. The mixture was heated to 90-95 ℃ and stirred for about 10min, and 8ppm Pt (chloroplatinic acid ethanol solution) was added. Maintaining the mixture in the bottle at 90-95 ℃ for 4 hours to obtain yellow transparent viscous liquid, wherein the viscous product is the rosin allyl ester modified organosilicon surfactant, and the average structure of the product is M 1 D 60 D 1 5 M 1 Wherein D is 1 The average structure is as follows:
a＝20，b＝20。
example 2
The embodiment of the invention provides a preparation method of bio-based polyether modified polysiloxane, which comprises the following steps:
into a 500ml three-necked flask equipped with a mechanical stirrerAdding 8.0g of 1, 3-tetramethyl disiloxane and 292.0g of octamethyl cyclotetrasiloxane, adding 0.2g of trifluoro-benzenesulfonic acid, stirring at 60-65 ℃ for 4h, and post-treating to obtain the product with average structure M H D 66 M H Hydrogen terminated polysiloxanes of (2).
36.0g of allyl rosin ester and 264.0g of hydrogen terminated polysiloxane M H D 66 M H The mixture was mixed, heated to 90 to 95℃and stirred for 10 minutes, and 8ppm of Pt (chloroplatinic acid in ethanol) was added. Maintaining the mixture in the bottle at 90-95 ℃ for 4h, and treating to obtain yellow transparent viscous liquid, wherein the average structural formula of the viscous product is M 1 D 66 M 1 I.e., allyl rosin ester terminated polysiloxanes.
283.6g of allyl rosin ester terminated polysiloxane M 1 D 66 M 1 Mixing with 16.4g tetramethyl tetra-four-hydrogen cyclosiloxane, adding 0.3g trifluoro-benzene sulfonic acid, stirring at 60-65 deg.C for 3h, post-treating to obtain the final product with average structure M 1 D 66 D H 5.5 M 1 Allyl rosin ester terminated low hydrogen containing polysiloxanes.
84.6g of the average structure M 1 D 66 D H 5.5 M 1 Is added to 200ppm of N, N-dimethylethanolamine, and stirred. The mixture was heated to 80-85 ℃ and stirred for about 10min, and 10ppm Pt (chloroplatinic acid ethanol solution) was added. Maintaining the mixture in the bottle at 80-85 ℃ for 3h to obtain yellow transparent viscous liquid, wherein the viscous product is the rosin allyl ester modified organosilicon surfactant, and the average structure of the product is M 1 D 66 D 1 5.5 M 1 。
Example 3
The embodiment of the invention provides a preparation method of bio-based polyether modified polysiloxane, which comprises the following steps:
9.7g of 1, 3-tetramethyldisiloxane and 290.3g of octamethyl cyclotetrasiloxane were placed in a 500ml three-necked flask equipped with a mechanical stirrer, 0.1g of trifluoromethanesulfonic acid was added, and the mixture was stirred at 70 to 75℃for 2 hours, followed by post-treatment to obtain an averageThe structure is M H D 54 M H Hydrogen terminated polysiloxanes of (2).
42.6g of allyl rosin ester and 257.4g of hydrogen terminated polysiloxane M H D 54 M H The mixture was mixed, heated to 90 to 95℃and stirred for 10 minutes, and 8ppm of Pt (chloroplatinic acid in ethanol) was added. Maintaining the mixture in the bottle at 90-95 ℃ for 3h, and treating to obtain yellow transparent viscous liquid, wherein the average structural formula of the viscous product is M 1 D 54 M 1 I.e., allyl rosin ester terminated polysiloxanes.
284.1g of allyl rosin ester terminated polysiloxane M 1 D 54 M 1 Mixing with 15.9g of tetramethyl tetrahydrocyclotetrasiloxane, adding 0.5g of trifluoro-benzenesulfonic acid, stirring at 55-60 ℃ for 3h, and post-treating to obtain the product with average structure M 1 D 54 D H 4.5 M 1 Allyl rosin ester terminated low hydrogen containing polysiloxanes.
86.3g of the average structure M 1 D 54 D H 4.5 M 1 106.8g of polyether A and 106.8g of polyether B, 100pm of N, N-dibutylethanolamine were added and stirred. The mixture was heated to 90-95 ℃ and stirred for about 10min, and 8ppm Pt (chloroplatinic acid ethanol solution) was added. Maintaining the mixture in the bottle at 90-95 ℃ for 2h to obtain yellow transparent viscous liquid, wherein the viscous product is the rosin allyl ester modified organosilicon surfactant, and the average structure of the product is M 1 D 54 D 1 4.5 M 1 。
Example 4
The embodiment of the invention provides a preparation method of bio-based polyether modified polysiloxane, which comprises the following steps:
into a 500ml three-necked flask equipped with a mechanical stirrer, 9.0g of 1, 3-tetramethyldisiloxane and 298.2g of octamethyl cyclotetrasiloxane were charged, 0.5g of trifluoromethanesulfonic acid was added, and the mixture was stirred at 60 to 65℃for 3 hours, followed by post-treatment to give an average structure of M H D 60 M H Hydrogen terminated polysiloxanes of (2).
39.4g of allyl hydrogenated rosin and 257.4g of end-hydrogen polysiliconeOxoalkane M H D 60 M H The mixture was mixed, heated to 80 to 85 ℃, stirred for 10 minutes, and 10ppm of Pt (chloroplatinic acid ethanol solution) was added. Maintaining the mixture in the bottle at 80-85 ℃ for 4h, and treating to obtain yellow transparent viscous liquid with an average structural formula of M 2 D 60 M 2 Namely hydrogenated rosin allyl ester terminated polysiloxane. Wherein the method comprises the steps of
285.4g of hydrogenated allyl rosin ester end-capped polysiloxane M 2 D 60 M 2 Mixing with 14.6g tetramethyl tetra-four-hydrogen cyclosiloxane, adding 0.1g trifluoro-benzene sulfonic acid, stirring at 70-75 deg.C for 2h, post-treating to obtain the final product with average structure M 2 D 60 D H 4.5 M 2 Allyl esters of hydrogenated rosin terminated low hydrogen containing polysiloxanes.
85.3g of the average structure M 2 D 60 D H 4.5 M 2 136.6g of polyether A and 78.1g of polyether B, 50ppm of N, N-dimethylethanolamine were added and stirred. The mixture was heated to 85-90 ℃ and stirred for about 10min, and 9ppm Pt (chloroplatinic acid ethanol solution) was added. Maintaining the mixture in the bottle at 85-90 ℃ for reaction for 5 hours to obtain yellow transparent viscous liquid, wherein the viscous product is hydrogenated rosin allyl ester modified organosilicon surfactant, and the average structure of the product is M 2 D 60 D 2 4.5 M 2 。
Wherein D is 2 The average structure is as follows:
a＝22，b＝22。
example 5
The embodiment of the invention provides a preparation method of bio-based polyether modified polysiloxane, which comprises the following steps:
500ml three to equipped with mechanical stirrer10.5g of 1, 3-tetramethyl disiloxane and 289.5g of octamethyl cyclotetrasiloxane are added into a neck flask, 1.2g of trifluoro-benzenesulfonic acid is added, and the mixture is stirred for 5 hours at the temperature of 40 to 45 ℃ and is subjected to post treatment to obtain the product with the average structure of M H D 50 M H Hydrogen terminated polysiloxanes of (2).
45.9g of allyl hydrogenated rosin ester and 254.1g of hydrogen terminated polysiloxane M H D 50 M H The mixture was mixed, heated to 95-100 ℃, stirred for 10min, and 6ppm Pt (chloroplatinic acid ethanol solution) was added. Maintaining the mixture in the bottle at 95-100deg.C, reacting for 3 hr to obtain yellow transparent viscous liquid with average structural formula M 2 D 50 M 2 Namely hydrogenated rosin allyl ester terminated polysiloxane.
281.4g of hydrogenated allyl rosin ester end-capped polysiloxane M 2 D 50 M 2 Mixing with 18.6g tetramethyl tetra-four-hydrogen cyclosiloxane, adding 0.9g trifluoro-benzene sulfonic acid, stirring at 50-60 deg.C for 3h, post-treating to obtain the final product with average structure M 2 D 50 D H 5 M 2 Allyl esters of hydrogenated rosin terminated low hydrogen containing polysiloxanes.
80.1g of the average structure M 2 D 60 D H 6 M 2 92.6g of polyether A and 127.3g of polyether B, 300ppm of N, N-dibutylethanolamine were added and stirred. The mixture was heated to 95-100 ℃ and stirred for about 10min, and 6ppm Pt (chloroplatinic acid ethanol solution) was added. Maintaining the mixture in the bottle at 95-100 ℃ for 5h to obtain yellow transparent viscous liquid, wherein the viscous product is the hydrogenated rosin allyl ester modified organosilicon surfactant, and the average structure of the product is M 2 D 50 D 3 5 M 2 。
Wherein D is 3 The average structure is as follows:
a＝19，b＝19。
example 6
The embodiment of the invention provides a preparation method of bio-based polyether modified polysiloxane, which comprises the following steps:
into a 500ml three-necked flask equipped with a mechanical stirrer, 7.0g of 1, 3-tetramethyldisiloxane and 270.6g of octamethyl cyclotetrasiloxane were charged, 1.0g of trifluoromethanesulfonic acid was added, and the mixture was stirred at 40 to 45℃for 5 hours, followed by post-treatment to give an average structure of M H D 70 M H Hydrogen terminated polysiloxanes of (2).
34.6g of allyl hydrogenated rosin ester and 265.8 g of hydrogen-terminated polysiloxane M are reacted H D 70 M H The mixture was mixed, heated to 95-100 ℃, stirred for 10min, and 8ppm of Pt (chloroplatinic acid ethanol solution) was added. Maintaining the mixture in the bottle at 95-100 ℃ for 2h, and treating to obtain yellow transparent viscous liquid with an average structural formula of M 2 D 70 M 2 Namely hydrogenated rosin allyl ester terminated polysiloxane.
277.8g of hydrogenated allyl rosin ester end-capped polysiloxane M 2 D 70 M 2 Mixing with 22.2g of tetramethyl tetrahydrocyclotetrasiloxane, adding 1.2g of trifluoro-benzenesulfonic acid, stirring at 40-45 ℃ for 5h, and post-treating to obtain the product with average structure M 2 D 70 D H 8 M 2 Allyl esters of hydrogenated rosin terminated low hydrogen containing polysiloxanes.
67.4g of the average structure M 2 D 70 D H 8 M 2 116.3g polyether A and 116.3g polyether B, 100ppm N, N-dimethylethanolamine was added and stirred. The mixture was heated to 90-95 ℃ and stirred for about 10min, and 10ppm Pt (chloroplatinic acid ethanol solution) was added. Maintaining the mixture in the bottle at 90-95 ℃ for 2h to obtain yellow transparent viscous liquid, wherein the viscous product is the rosin allyl ester modified organosilicon surfactant, and the average structure of the product is M 2 D 70 D 1 8 M 2 。
Comparative example 1
This comparative example provides a process for preparing polyether modified polysiloxanes comprising:
into a 500ml four-necked flask equipped with a mechanical stirrer and a dry nitrogen line was charged 78.0g of polysiloxane (average formula: MD) 60 D H 5.0 M), 111.0g of polyether A,111.0g of polyether B, 200ppm of N, N-dibutylethanolamine were added and stirred. The mixture was heated to 90-95 ℃ and stirred for about 10min, and 8ppm Pt (chloroplatinic acid ethanol solution) was added. After maintaining the mixture in the bottle at 90-95℃for one hour, the Si-H content of the mixture was determined to be less than 0.2mL/g. A yellow transparent viscous liquid was obtained. The viscous product was the silicone surfactant prepared in comparative example 1. The product has an average structural formula of MD 60 D 1 5 M, where m= (CH 3 ) 3 Si-，D 1 The average structure is as follows:
a＝20，b＝20。
comparative example 2
This comparative example provides a process for preparing polyether modified polysiloxanes comprising:
into a 500ml four-necked flask equipped with a mechanical stirrer and a dry nitrogen line was charged 78.0g of polysiloxane (average formula: MD) 60 D H 5.0 M), 111.0g of polyether A,111.0g of polyether B,1.0g of allyl rosin ester, 200ppm of N, N-dibutylethanolamine were added and stirred. The mixture was heated to 90-95 ℃ and stirred for about 10min, and 8ppm Pt (chloroplatinic acid ethanol solution) was added. After maintaining the mixture in the bottle at 90-95℃for one hour, the Si-H content of the mixture was determined to be less than 0.2mL/g. A yellow transparent viscous liquid was obtained. The viscous product was the silicone surfactant prepared in comparative example 2. The product has an average structural formula of MD 60 D 1 4.9 D 4 0.1 M, where m= (CH 3 ) 3 Si-，D 4 The structure is as follows:D 1 average structureThe method comprises the following steps:
a＝20，b＝20。
comparative example 3
This comparative example provides a process for preparing polyether modified polysiloxanes comprising:
into a 500ml four-necked flask equipped with a mechanical stirrer and a dry nitrogen line was charged 78.0g of polysiloxane (average formula: MD) 54 D H 4.5 M), 111.0g of polyether A,111.0g of polyether B,1.0g of hydrogenated rosin allyl ester, 200ppm of N, N-dibutylethanolamine were added and stirred. The mixture was heated to 90-95 ℃ and stirred for about 10min, and 8ppm Pt (chloroplatinic acid ethanol solution) was added. After maintaining the mixture in the bottle at 90-95℃for one hour, the Si-H content of the mixture was determined to be less than 0.2mL/g. A yellow transparent viscous liquid was obtained. The viscous product was the silicone surfactant prepared in comparative example 3. The product has an average structural formula of MD 54 D 1 4.4 D 5 0.1 M, where m= (CH 3 ) 3 Si-，D 5 The structure is as follows:D 1 the average structure is as follows:
a＝20，b＝20。
comparative example 4
This comparative example provides a process for preparing polyether modified polysiloxanes comprising:
into a 500ml four-necked flask equipped with a mechanical stirrer and a dry nitrogen line was charged 78.0g of polysiloxane (average formula: MD) 60 D H 5.0 M), 111.0g of polyether A,111.0g of polyether B,3.0g of allyl rosin, 200ppm of N, N-dibutylethyl acetate were addedAlcohol amine and stirring. The mixture was heated to 90-95 ℃ and stirred for about 10min, and 8ppm Pt (chloroplatinic acid ethanol solution) was added. Maintaining the temperature of the mixture in the bottle at 90-95 ℃, preserving the temperature for 5 hours to obtain turbid viscous liquid, and layering the system after standing.
Comparative example 5
This comparative example provides a process for preparing polyether modified polysiloxanes comprising:
into a 500ml four-necked flask equipped with a mechanical stirrer and a dry nitrogen line was charged 78.0g of polysiloxane (average formula: MD) 66 D H 5.5 M), 107.7g of polyether A,107.7g of polyether B,3.0g of hydrogenated rosin allyl ester, 200ppm of N, N-dibutylethanolamine were added and stirred. The mixture was heated to 90-95 ℃ and stirred for about 10min, and 8ppm Pt (chloroplatinic acid ethanol solution) was added. Heating the mixture in the bottle to 100-105 ℃, preserving heat for 6 hours to obtain turbid viscous liquid, and layering the system after standing.
Comparative example 6
This comparative example provides a process for preparing polyether modified polysiloxanes comprising:
into a 500ml three-necked flask equipped with a mechanical stirrer, 9.0g of 1, 3-tetramethyldisiloxane and 298.2g of octamethyl cyclotetrasiloxane were charged, 0.3g of trifluoromethanesulfonic acid was added, and the mixture was stirred at 60 to 65℃for 3 hours, followed by post-treatment to give an average structure of M H D 60 M H Hydrogen terminated polysiloxanes of (2).
46.0g of allyl cardanolAnd 251.0g of hydrogen-terminated polysiloxanes M H D 60 M H The mixture was mixed, heated to 90 to 95℃and stirred for 10 minutes, and 10ppm of Pt (chloroplatinic acid ethanol solution) was added. The mixture in the bottle is maintained at 90-95 ℃ for reaction for 4 hours, and the treated sample is turbid.
As can be seen from the above examples and comparative examples, when the copolymer is synthesized by directly using the bio-base and polyether as reactants, the amount of the bio-base used is greatly limited, and the bio-base content in the product is low. The bio-based content of the bio-based-containing polyether modified polysiloxane provided by the embodiment of the invention is obviously improved, as shown in table 1.
Comparison of Biomass content in Table 1 System
| Examples | Biobased content (wt%) |
| Example 1 | 3.47 |
| Example 2 | 3.19 |
| Example 3 | 3.79 |
| Example 4 | 3.46 |
| Example 5 | 4.04 |
| Example 6 | 3.03 |
| Comparative example 1 | 0 |
| Comparative example 2 | 0.33 |
| Comparative example 3 | 0.33 |
As shown in Table 1, the bio-based content of the bio-based-containing polyether modified polysiloxane provided by the embodiment of the invention is improved from 0.33% to more than 3%, so that the order of magnitude is improved. The copolymers of comparative examples 4 and 5 were synthesized by increasing the amount of the bio-base to be co-grafted with the allyl polyether on the polysiloxane main chain in order to increase the content of the bio-base in the copolymer, but after increasing the amount of the bio-base (comparative example 4 using allyl rosin ester and comparative example using allyl hydrogenated rosin ester), the reaction was not normally carried out, and the copolymer exhibited a cloudy state. Comparative example 6 using a biobased compound having a hydroxyl group, when the biobased compound is grafted in the second step, the normal reaction of hydrosilylation is affected, resulting in that the copolymer is not synthesized smoothly.
Application example
Preparation of Bio-based polyurethane Soft foam Using the bio-based polyether modified polysiloxanes of examples 1 to 6 and the polyether modified polysiloxanes of comparative examples 1 to 3, respectively, the specific formulation is shown in Table 2, and the density of the prepared bio-based polyurethane Soft foam is 25.0kg/m 3 。
TABLE 2 Density of 25.0kg/m 3 Formulation of bio-based polyurethane flexible foam
| Raw materials | Proportion (wt%) |
| PPG | 60.0 |
| Bio-based polyols | 40.0 |
| Water and its preparation method | 3.8 |
| Amine A33 | 0.16～0.17 |
| Stannous octoate | 0.19～0.20 |
| TDI80/20 (index 110) | 54.37 |
| The products of examples 1 to 6 or comparative examples 1 to 6 | 1.0～1.1 |
Wherein the polyol PPG is a polyol prepared from a mixture of 84-88% by weight of propylene oxide and 12-16% by weight of ethylene oxide, and has a hydroxyl value of 56mgKOH/g.
The bio-based polyol is castor oil-based polyol, and has a hydroxyl value of 120mgKOH/g.
TDI80/20 was a mixture of 80% by mass of 2, 4-toluene diisocyanate and 20% by mass of 2, 6-toluene diisocyanate.
A33 is a mixture of 33% by mass of triethylenediamine and 67% by mass of dipropylene glycol.
The preparation method of the bio-based polyurethane flexible foam comprises the following steps:
300.0+/-0.5 g of polyol PPG, 200.0+/-0.5 g of bio-based polyol is added into a 2000ml plastic cup, and the temperature of the polyol is controlled to be maintained at 21.5-22.5 ℃; adding 19.00+ -0.02 g of water, 5.00-5.50 g of the silicone surfactant of examples 1-6 or comparative examples 1-6, and 0.80-0.85 g of A-33, and stirring the mixture at 2000r/m for 20s; adding 0.95-1.00 g stannous octoate, and stirring for 20s at 2000 r/m; pouring 271.85 +/-0.20 g of TDI with the temperature maintained at 21.5-22.5 ℃ and stirring for 7s at 2000r/m, pouring the mixture into a cube mould with the thickness of 28.5cm and the thickness of 28.5cm, and keeping the plastic cup inverted and continuously pouring for 7s. The foam starts to react and rises continuously, the highest rising height, the foam jumping time and the retracted height of the foam are recorded, and the foam is stood. The foam is cured in an oven at 80-100 ℃ for 1h for a total of 200s from the step of mixing TDI; the foam was taken out of the oven and cooled for at least 2h.
All polyurethane flexible foams were prepared with the same formulation as described above, the main difference between the examples being the use of the surfactant of the examples in place of another surfactant.
The polyurethane flexible foam was evaluated by the following performance test:
indentation hardness: sample preparation and testing methods refer to GB/T10807-2006 determination of Soft foam Polymer Material-hardness (indentation method);
rebound rate: sample preparation and testing methods refer to GB/T6670-2008 "determination of resilience of Soft foam Polymer Material-falling ball method";
tensile strength: sample preparation and testing methods are described in GB/T6344-2008 determination of tensile Strength and elongation at break of Soft foam Polymer materials.
Tear strength: sample preparation and testing methods are described in GB/T10808-2006 "determination of tear Strength of high Polymer porous elastic Material".
The polyurethane flexible foam preparation was performed according to the standard except that the silicone surfactant was changed, and the prepared foam was analyzed and compared, and the results are shown in table 3 below.
TABLE 3 results of performance testing of biobased polyurethane flexible foams
As can be seen from Table 3, the bio-based polyether modified polysiloxanes of examples 1 to 6 provided in the examples of the present invention have remarkably superior properties in indentation hardness, rebound resilience, tensile strength and tear strength as compared with the silicone surfactants of comparative examples 1 to 3.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A bio-based polyether modified polysiloxane is characterized by having the following structural formula:
wherein m=45-75, n=3-10;
r1 and R3 each independently represent a bio-based group derived from a bio-based substance having a terminal double bond and containing no hydroxyl group therein;
r2 represents-CH 2 CH 2 CH 2 (OC 2 H 4 ) a (OC 3 H 6 ) b OR4, wherein a=10-30, b=10-30,
r4 is H or alkyl containing 1-4 carbon atoms.
2. The bio-based polyether modified polysiloxane according to claim 1, wherein the bio-based material is selected from the group consisting of rosin alkene esters or alkenyl-containing monoterpenes;
preferably, the rosin allyl ester compound is selected from at least one of rosin allyl ester, hydrogenated rosin allyl ester, rosin allyl methyl ester, hydrogenated rosin allyl methyl ester, rosin allyl ethyl ester and hydrogenated rosin allyl ethyl ester;
preferably, the alkenyl-containing monoterpene compound comprises an alkenyl-containing monocyclic monoterpene compound; more preferably limonene;
more preferably, the bio-based groups are grafted to the siloxane backbone by hydrosilylation.
3. A method of preparing the bio-based polyether modified polysiloxane according to claim 1, comprising: reacting the terminal hydrogen-containing polysiloxane with a bio-based substance under the action of a catalyst to form polysiloxane with a terminal group containing a bio-base;
then, the polysiloxane with the end group containing the biological group and tetramethyl tetrahydrocyclotetrasiloxane are subjected to acid catalysis to form low hydrogen polysiloxane containing the biological group;
the biobased low hydrogen containing polysiloxane and the terminal allyl polyether are then mixed to react to form the biobased polyether modified polysiloxane.
4. A method of preparing according to claim 3, wherein the step of forming the end group bio-based containing polysiloxane comprises: mixing the hydrogen-containing polysiloxane, the bio-based material and the catalyst, and reacting for 2-6 hours at 80-100 ℃;
preferably, the mass percent of the hydrogen-containing polysiloxane at the end and the bio-based substance is 11-7:89-93;
preferably, the catalyst is selected from complexes containing at least one of palladium, rhodium and platinum; preferably chloroplatinic acid;
preferably, the catalyst is used in an amount of 5 to 10ppm.
5. The method of preparing according to claim 3, wherein the step of forming the biobased low hydrogen containing polysiloxane comprises: mixing polysiloxane with the end group containing biological groups, tetramethyl tetrahydrocyclotetrasiloxane and an acid catalyst, and reacting for 2-6 hours at 40-80 ℃;
preferably, the mass percentage ratio of the end group containing bio-based polysiloxane to the tetramethyl-tetrahydrocyclotetrasiloxane is 92-96:8-4;
preferably, the acid catalyst is selected from at least one of acid clay, sulfuric acid, and trifluoro-benzenesulfonic acid;
preferably, the acid catalyst is used in an amount of 0.1 to 1.5% of the total amount of raw materials forming the bio-based low hydrogen containing polysiloxane.
6. A method of preparing according to claim 3, wherein the step of forming the bio-based polyether modified polysiloxane comprises: mixing the low-hydrogen polysiloxane containing biological base, terminal allyl polyether, amine auxiliary agent and catalyst, and reacting for 2-6 hours at 80-100 ℃;
preferably, the mass percent ratio of the terminal allyl polyether to the biobased low hydrogen-containing polysiloxane is 80-70:20-30;
preferably, the catalyst is selected from complexes containing at least one of palladium, rhodium and platinum; preferably chloroplatinic acid;
preferably, the catalyst is used in an amount of 5 to 10ppm;
preferably, the amine auxiliary agent is selected from at least one of N, N-dimethylethanolamine, N-dibutylethanolamine, 3-dimethylpropylamine and 2-butylaminoethanol;
preferably, the amine adjuvant is used in an amount of 50-500ppm.
7. A method of preparing as claimed in claim 3 wherein the step of forming the hydrogen terminated polysiloxane comprises: mixing octamethyl cyclotetrasiloxane, 1, 3-tetramethyl disiloxane and an acid catalyst, and reacting for 2-6 hours at 40-80 ℃;
preferably, the mass percent ratio of the octamethyl cyclotetrasiloxane and the 1, 3-tetramethyl disiloxane is 2-4:98-96;
preferably, the acid catalyst is selected from at least one of acid clay, sulfuric acid, and trifluoro-benzenesulfonic acid;
preferably, the acid catalyst is used in an amount of 0.1 to 1.5% of the total amount of raw materials forming the hydrogen-terminated polysiloxane.
8. A foam stabilizer comprising the bio-based polyether modified polysiloxane according to claim 1 as a raw material.
9. A polyurethane foam comprising a polyol, the bio-based polyether modified polysiloxane of claim 1 or the foam stabilizer of claim 8 as a raw material.
10. The polyurethane foam of claim 9, wherein the polyurethane foam is a flexible polyurethane foam;
preferably, the mass percent ratio of the polyol to the bio-based polyether modified polysiloxane is 40:1.0-1.1;
preferably, the hydroxyl number of the polyol is from 30 to 80mgKOH/g, preferably from 45 to 65mgKOH/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311583838.3A CN117659409A (en) | 2023-11-24 | 2023-11-24 | Bio-based polyether modified polysiloxane, preparation method thereof, foam stabilizer and polyurethane foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311583838.3A CN117659409A (en) | 2023-11-24 | 2023-11-24 | Bio-based polyether modified polysiloxane, preparation method thereof, foam stabilizer and polyurethane foam |
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| CN117659409A true CN117659409A (en) | 2024-03-08 |
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| CN202311583838.3A Pending CN117659409A (en) | 2023-11-24 | 2023-11-24 | Bio-based polyether modified polysiloxane, preparation method thereof, foam stabilizer and polyurethane foam |
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| Country | Link |
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| CN (1) | CN117659409A (en) |
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2023
- 2023-11-24 CN CN202311583838.3A patent/CN117659409A/en active Pending
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