CN108610466A - A kind of polyurea elastomer and preparation method thereof substituting polyethers completely with polysiloxanes - Google Patents
A kind of polyurea elastomer and preparation method thereof substituting polyethers completely with polysiloxanes Download PDFInfo
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- CN108610466A CN108610466A CN201810470625.2A CN201810470625A CN108610466A CN 108610466 A CN108610466 A CN 108610466A CN 201810470625 A CN201810470625 A CN 201810470625A CN 108610466 A CN108610466 A CN 108610466A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6529—Compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
Abstract
The present invention relates to a kind of polyurea elastomer and preparation method thereof substituting polyethers completely with polysiloxanes, and preparation method includes step:(1) in the in the mixed solvent of organic solvent A and B, it is separately added into the dimethyl silicone polymer C and diisocyanate cpd of the amine propyl sealing end of calculation amount, at 0 50 DEG C, 10 80min are stirred to react, generate the prepolymer D of isocyanate-terminated low molecular weight;(2) the prepolymer D generated in step (1) at 0 30 DEG C is reacted into 10 500min with end amine compound, obtains the mixed solution of the polyurea polymer containing polysiloxane;Then volatilization removal solvent to get.The present invention reduces micron-scale phase separation sharp between soft segment and hard section using mixed solvent and by regulating and controlling the dimethyl silicone polymer molecular weight of amine propyl sealing end, to greatly improve the mechanical property of elastomer.
Description
Technical field
The present invention relates to a kind of polyurea elastomer and preparation method thereof substituting polyethers completely with polysiloxanes, belong to
It is the synthesis technical field of organosilicon macromolecule material.
Background technology
Polysiloxanes is to collectively constitute its unique molecular structure by Si-O-Si main chains and organic base side chain, collects organic-nothing
, with extremely low glass transition temperature (- 123 DEG C), high-low temperature resistant, resistance to oxidation is weather-proof for machine double grading and function
Property, the excellent properties such as low-surface-energy and good hydrophobicity.
Thermoplastic poly urea elastomers (TPU) are a series of elasticity that there is remarkable mechanical property to become reconciled, and strong hardness is resistance to
The multiphase block polymer of abrasion and chemical resistance.Polysiloxanes-the polyurea elastomer prepared using polysiloxanes as soft chain segment
The excellent properties of both polysiloxane and polyureas are had both, the defect of polysiloxanes poor mechanical property has both been overcome, has also compensated for
The deficiency of polyureas weatherability difference, in terms of building trade, automotive trim, technical field of biological material and clothing industry suffer from extensively
Application.
The mechanical property of these certain polysiloxanes-polyurea elastomer be still nothing like it is traditional by polyethers as soft chain
Polyureas prepared by section.The micron-scale phase separation of soft segment and hard section, which is thermoplasticity polyureas elasticity, has the reason of high stable modulus, still
Due to the solubility parameters (15.6 (Jcm of dimethyl silicone polymer-3)1/2) and polyureas solubility parameters (45.6 (Jcm-3)1/2) difference
It is excessive, polyureas is prepared by soft chain segment of polysiloxanes, may cause to generate phase separation macroscopically in reaction, make it that can not give birth to
At the polymer of macromolecule, and then influence its mechanical property.It is prepared or even without the phase separation formed macroscopically
Polymer mutually assembles the boundary of phase and also will produce sharp microphase-separated in polysiloxanes aggregation with polyureas, this sharp
Boundary also results in the effect that pulling force is shifted from soft chain segment region to hard segment domains and reduces, and the mechanics for affecting elastomer is strong
Degree.
In order to avoid sharp micron-scale phase separation, traditional method is to be used in mixed way polysiloxanes and polyethers.Polyethers
Solubility parameters is 23.5 (Jcm-3)1/2, the interaction of urea groups and ether can (19.2kJmol-1) it is more than the boundary of urea groups and siloxanes
It face can (7.5kJmol-1).Transitional face can be formed between polysiloxanes and polyureas in this way, reduces microphase-separated.Specific method
Mostly be preparation polyurea elastomer is reacted with isocyanate compound again using amino-terminated polysiloxanes to be blended with polyethers, but
This method still can not avoid the connection of the compound of polysiloxanes and isocyanates, can not avoid sharp microphase-separated with
And the influence of the mechanical property to elastomer, while the introducing of polyethers also can influence the excellent properties of polysiloxanes in the elastomer
Performance.Meanwhile the thermoplastic elastomer (TPE) performance that this method obtains is unstable, material property poor reproducibility greatly restricts
The popularization and application of this method.
Chinese patent document CN103360562A discloses a kind of polysiloxanes-polyureas-polyurethanes gelinite material
Preparation method for material.By 100-200 parts of polysiloxanes, diisocyanate at a temperature of 60 DEG C -90 DEG C with 70-160 parts, stirring
1-3h is reacted, the terminal isocyanate group semi-prepolymer A that isocyanate group relative mass percentage composition is 15%-25% is prepared;
By terminal isocyanate group semi-prepolymer A and Amino End Group compound is uniformly mixed, cast prepares the poly- ammonia of polysiloxanes-polyureas-
Carbamate gel material;Wherein terminal isocyanate group semi-prepolymer A30-60 mass parts, Amino End Group compound 100-400 matter
Measure part.Using hydroxy-end capped polysiloxanes in the patent document, reactivity is low, so reaction required temperature is excessively high,
Reaction time is also longer.And include amine terminated polyether in Amino End Group compound used, so still having traditional poly- silica
The shortcomings that alkane-polyethers-polyureas.
It there is no a kind of method that can not only avoid sharp phase separation at present, but also do not interfere with the excellent properties of polysiloxanes
It plays, to improve the mechanical property of polysiloxanes polyurea elastomer.
For this purpose, proposing the present invention.
Invention content
In view of the deficiencies of the prior art, the present invention provide a kind of polyurea elastomer substituting polyethers completely with polysiloxanes and
Preparation method.Use mixed solvent as the reaction dissolvent for preparing polyurea elastomer, being used in mixed way of two kinds of solvents can allow soft
Section is preferably dissolved in system with hard section, avoids that phase separation macroscopically occurs in reaction, so that it is guaranteed that generating macromolecular
The polymer of amount.Select the dimethyl silicone polymer that the amine propyl of suitable molecular weight blocks poly- for synthesizing as soft chain segment simultaneously
Urea elastomers reduce micron-scale phase separation sharp between soft segment and hard section, to greatly improve elasticity by regulatory molecule amount
The mechanical property of body.
Technical solution of the present invention is as follows:
A kind of polyurea elastomer substituting polyethers completely with polysiloxanes, the elastomer have general formula shown in formula (I):
Wherein n, m are the integer more than or equal to 1;
X isOr
CH2CH2CH2CH2CH2CH2;
Y is CH2CH2、CH2CH(CH3)CH2CH2CH2、CH2CH2CH2CH2CH2CH2Or
, according to the invention it is preferred to, 1≤n≤150,1≤m≤50.
According to the present invention, the preparation method of the above-mentioned polyurea elastomer for substituting polyethers completely with polysiloxanes, including step
It is as follows:
(1) in the in the mixed solvent of organic solvent A and B, it is separately added into the dimethyl silicone polymer C and two of amine propyl sealing end
Isocyanate compound is stirred to react 10-80min at 0-50 DEG C, generates the pre-polymerization of isocyanate-terminated low molecular weight
Object D;
(2) the prepolymer D generated in step (1) is reacted into 10-500min at 0-30 DEG C with end amine compound, obtained
Mixed solution containing polysiloxane-polyurea polymer;Then volatilization removal solvent is to get poly- to being substituted completely with polysiloxanes
The polyurea elastomer of ether.
Preparation in accordance with the present invention, it is preferred that organic solvent A described in step (1) be dimethylbenzene, tetrahydrofuran,
Dimethyl sulfoxide (DMSO), toluene, acetone, hexamethylene or dioxane;
Preferably, the organic solvent B is ether, dichloromethane, ethyl acetate, isopropanol or n-hexane;
Preferably, organic solvent A, the volume ratio of B are (5-15):1.
Preparation in accordance with the present invention, it is preferred that the dimethyl silicone polymer C of the amine propyl sealing end described in step (1)
With general formula shown in formula (II):
In formula (II), the value of n is identical as formula (I);
It is further preferred that the relative molecular weight ranging from 1000- of the dimethyl silicone polymer C of amine propyl sealing end
10000g/mol。
Preparation in accordance with the present invention, it is preferred that the diisocyanate cpd described in step (1) is toluene diisocyanate
Acid esters, methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, hexamethylene diisocyanate, methylcyclohexyl two are different
Cyanate, dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate, paraphenylene diisocyanate, terephthalylidene
Diisocyanate or tetramethylxylylene diisocyanate;
Further preferably methyl diphenylene diisocyanate, hexamethylene diisocyanate, two isocyanide of methylcyclohexyl
Acid esters or dicyclohexyl methyl hydride diisocyanate.
Preparation in accordance with the present invention, it is preferred that the dimethyl silicone polymer C of the amine propyl sealing end described in step (1)
Amino End Group and diisocyanate cpd in isocyanate group molar ratio be 1:(2-15), further preferably 1:(3-8).
Mole of the dimethyl silicone polymer C and isocyanate group in diisocyanate cpd of amine propyl sealing end of the present invention
The mechanical property for comparing final elastomer has a major impact, beyond the scope of this invention all the mechanical property of elastomer to be made bright
It is aobvious to decline.
Preparation in accordance with the present invention, it is preferred that reaction temperature is 5-40 DEG C in step (1), reaction time 10-
50min.Such as formula (III) institute of the prepolymer D general structures of isocyanate-terminated low molecular weight made from step (1) of the present invention
Show:
Preparation in accordance with the present invention, it is preferred that end amine compound described in step (2) be ethylenediamine, hexamethylene diamine,
Bis- (2- aminophenyls the are thio) ethane of bis- (p-aminobenzoic acid) propylene glycol esters, 1,2-, 2- methyl-1s, 5- pentanediamines, 3,5- bis-
Amino -4- trifluoromethyls phenetole or 4,4 '-di-2-ethylhexylphosphine oxides (2- ethyl 6- methyl cyclohexylamines).
Preparation in accordance with the present invention, it is preferred that reaction temperature described in step (2) is 0-15 DEG C, and the reaction time is
5-20min。
Preparation in accordance with the present invention, it is preferred that the time of step (2) solvent flashing at room temperature, solvent flashing is 2-
48h。
What the present invention did not elaborated is state of the art.
Beneficial effects of the present invention:
1, the present invention using amine propyl sealing end dimethyl silicone polymer C as soft chain segment A and B mixed solvent condition
The polyurea elastomer of lower preparation is preferably dissolved in system by soft segment and hard section using mixed solvent, reacts progress faster
More thoroughly, reaction rate is substantially increased.
2, the present invention selects the dimethyl silicone polymer C of the amine propyl sealing end of suitable molecular weight to be used to synthesize as soft chain segment
Polyurea elastomer reduces micron-scale phase separation sharp between soft segment and hard section, to greatly improve the mechanical property of elastomer,
Mechanical strength higher, tensile strength is up to 21MPa.
3, reaction process of the present invention is simpler, using minimum raw material, you can obtains the superior elastomer of tensile property.
Description of the drawings
Fig. 1 is the infrared spectrum of the polyurea elastomer obtained for substituting polyethers completely with polysiloxanes of the embodiment of the present invention 1.
Specific implementation mode
With reference to embodiment, the present invention will be further described, and following embodiments are illustrative, are not restrictive,
Protection scope of the present invention cannot be limited with following embodiments.
Raw materials used in embodiment is regular market purchase product.
The dimethyl silicone polymer C of amine propyl sealing end described in embodiment is prepared as follows to obtain:
In the four-hole boiling flask equipped with thermometer, spherical condensation tube, mechanical agitation and nitrogen access equipment, calculation amount is added
D4, α, ω-amine disiloxane and micro KOH solid powders.Under mechanical stirring by system, oil bath heating heats up
To 80-120 DEG C, balanced reaction 8 hours.After the completion of reaction, stop heating, be added with the glacial acetic acid of added KOH equimolar amounts into
Row neutralization reaction carries out vacuum distillation operation, steams low-boiling-point substance.Filtering product obtains the polydimethylsiloxanes of amine propyl sealing end
Alkane.
Embodiment 1,
A kind of preparation method for the polyurea elastomer substituting polyethers completely with polysiloxanes, including steps are as follows:
In the four-hole boiling flask equipped with constant pressure funnel, drying tube, mechanical agitation and nitrogen access equipment, 30g is added
Dicyclohexyl methyl hydride diisocyanate, dimethylbenzene and isopropanol (volume ratio 6 is used in combination:1) mixed solvent dissolving is complete, by force
Under strong stirring, the dimethyl silicone polymer C dissolvings that the amine propyl that the molecular weight of 70g is 4000 blocks are passed through into dropping liquid later completely
Funnel is added drop-wise to dropwise in above-mentioned solution, reacts 30min at 40 DEG C, prepares prepolymer D, finally by 20g2- methyl-1s, 5- penta
Diamines is dissolved in mixed solution, is added dropwise in reactor by dropping funel, reacts 10min at 5 DEG C, and product is poured into mold
In, volatilization removal solvent, obtains elastomer at room temperature.
Obtained elastomer structure is as follows:
Mechanics Performance Testing is carried out to it, it is 21MPa, elongation at break 100% to draw high intensity.
The infrared spectrum of the present embodiment polyurea elastomer obtained for substituting polyethers completely with polysiloxanes is as shown in Figure 1.
Embodiment 2,
A kind of preparation method for the polyurea elastomer substituting polyethers completely with polysiloxanes, including steps are as follows:
In the four-hole boiling flask equipped with constant pressure funnel, drying tube, mechanical agitation and nitrogen access equipment, 20g is added
Methyl diphenylene diisocyanate, tetrahydrofuran and dichloromethane (volume ratio 8 is used in combination:1) mixed solvent dissolving is complete,
Under strong stirring, pass through drop after the dimethyl silicone polymer C that the amine propyl that the molecular weight of 60g is 2000 blocks is dissolved completely
Liquid funnel is added drop-wise to dropwise in above-mentioned solution, reacts 10min at 30 DEG C, prepares prepolymer D, is finally dissolved in 20g hexamethylene diamines
It in mixed solution, is added dropwise in reactor by dropping funel, reacts 15min at 10 DEG C, product is poured into mold, room temperature
Lower volatilization removes solvent, obtains elastomer.
Obtained elastomer structure is as follows:
Mechanics Performance Testing is carried out to it, it is 20MPa, elongation at break 110% to draw high intensity.
Embodiment 3,
A kind of preparation method for the polyurea elastomer substituting polyethers completely with polysiloxanes, including steps are as follows:
In the four-hole boiling flask equipped with constant pressure funnel, drying tube, mechanical agitation and nitrogen access equipment, 30g is added
Dicyclohexyl methyl hydride diisocyanate, dimethyl sulfoxide (DMSO) and n-hexane (volume ratio 8 is used in combination:1) mixed solvent has dissolved
Entirely, it under strong stirring, is dripped dropwise by dropping funel after the block copolymer A that the molecular weight of 70g is 3000 is dissolved completely
It is added in above-mentioned solution, reacts 20min at 40 DEG C, prepare prepolymer D, finally by 4,4 '-di-2-ethylhexylphosphine oxides of 20g (2- ethyls 6-
Methyl cyclohexylamine) it is dissolved in mixed solution, it is added dropwise in reactor by dropping funel, reacts 20min at 10 DEG C, by product
It pours into mold, volatilization removal solvent, obtains elastomer at room temperature.
Mechanics Performance Testing is carried out to it, it is 18MPa, elongation at break 120% to draw high intensity.
Embodiment 4,
A kind of preparation method for the polyurea elastomer substituting polyethers completely with polysiloxanes, including steps are as follows:
In the four-hole boiling flask equipped with constant pressure funnel, drying tube, mechanical agitation and nitrogen access equipment, 20g is added
Methyl diphenylene diisocyanate, toluene and n-hexane (volume ratio 5 is used in combination:1) mixed solvent dissolving is complete, stirs strongly
It mixes down, the dimethyl silicone polymer C dissolvings that the amine propyl that the molecular weight of 60g is 5000 blocks is passed through into dropping funel later completely
It is added drop-wise to dropwise in above-mentioned solution, reacts 30min at 40 DEG C, prepare prepolymer D, it is molten that 20g ethylenediamines are finally dissolved in mixing
In liquid, it is added dropwise in reactor at 10 DEG C by dropping funel and reacts 10min, product is poured into mold, is volatilized at room temperature
Solvent is removed, elastomer is obtained.
Mechanics Performance Testing is carried out to it, it is 19MPa to draw high intensity.Elongation at break is 120%.
Embodiment 5,
A kind of preparation method for the polyurea elastomer substituting polyethers completely with polysiloxanes, including steps are as follows:
In the four-hole boiling flask equipped with constant pressure funnel, drying tube, mechanical agitation and nitrogen access equipment, 30g is added
Dicyclohexyl methyl hydride diisocyanate, toluene and isopropanol (volume ratio 5 is used in combination:1) mixed solvent dissolving is complete, strongly
Under stirring, the dimethyl silicone polymer C dissolvings that the amine propyl that the molecular weight of 60g is 2000 blocks are leaked by dropping liquid later completely
Bucket is added drop-wise to dropwise in above-mentioned solution, is reacted 30min at 30 DEG C, is prepared prepolymer D, 20g hexamethylene diamines are finally dissolved in mixing
It in solution, is added dropwise in reactor by dropping funel, reacts 10min at 20 DEG C, product is poured into mold, wave at room temperature
Hair removal solvent, obtains elastomer.
Mechanics Performance Testing is carried out to it, it is 20MPa, elongation at break 100% to draw high intensity.
Comparative example 1,
A kind of preparation method for the polyurea elastomer substituting polyethers completely with polysiloxanes, including steps are as follows:
In the four-hole boiling flask equipped with constant pressure funnel, drying tube, mechanical agitation and nitrogen access equipment, 30g is added
Dicyclohexyl methyl hydride diisocyanate, be used in combination toluene solvant complete, under strong stirring, the amine for being 4000 by the molecular weight of 70g
It is added drop-wise to dropwise in above-mentioned solution by dropping funel after the dimethyl silicone polymer C dissolvings completely of propyl sealing end, at 40 DEG C
30min is reacted, prepares prepolymer D, finally by 20g2- methyl-1s, 5- pentanediamines are dissolved in mixed solution, pass through dropping funel
It is added dropwise in reactor, reacts 10min at 5 DEG C, product is poured into mold, volatilization removal solvent, obtains elasticity at room temperature
Body.
Mechanics Performance Testing is carried out to it, it is 4MPa, elongation at break 110% to draw high intensity.
This comparative example is generated since single solvent can not fully dissolve soft segment with hard section in reaction using single solvent
Macroscopical phase separation, makes the reaction can not carry out thoroughly, affecting the mechanical property of product.
Comparative example 2,
A kind of preparation method for the polyurea elastomer substituting polyethers completely with polysiloxanes, including steps are as follows:
In the four-hole boiling flask equipped with constant pressure funnel, drying tube, mechanical agitation and nitrogen access equipment, 40g is added
Methyl diphenylene diisocyanate, tetrahydrofuran and dichloromethane (volume ratio 8 is used in combination:1) mixed solvent dissolving is complete,
Under strong stirring, pass through drop after the dimethyl silicone polymer C that the amine propyl that the molecular weight of 60g is 2000 blocks is dissolved completely
Liquid funnel is added drop-wise to dropwise in above-mentioned solution, reacts 10min at 30 DEG C, prepares prepolymer D, is finally dissolved in 20g hexamethylene diamines
It in mixed solution, is added dropwise in reactor by dropping funel, reacts 15min at 10 DEG C, product is poured into mold, room temperature
Lower volatilization removes solvent, obtains elastomer.
Mechanics Performance Testing is carried out to it, it is 3MPa to draw high intensity.Elongation at break is 90%.
Isocyanide in the Amino End Group and diisocyanate cpd of the dimethyl silicone polymer C that amine propyl blocks in this comparative example
The ratio of perester radical is too low (methyl diphenylene diisocyanate addition is excessive), causes mechanics of elastic bodies performance not high.
Comparative example 3,
A kind of preparation method for the polyurea elastomer substituting polyethers completely with polysiloxanes, including steps are as follows:
In the four-hole boiling flask equipped with constant pressure funnel, drying tube, mechanical agitation and nitrogen access equipment, 30g is added
Dicyclohexyl methyl hydride diisocyanate, dimethyl sulfoxide (DMSO) and n-hexane (volume ratio 8 is used in combination:1) mixed solvent has dissolved
Entirely, logical after the dimethyl silicone polymer C dissolvings completely that the amine propyl that the molecular weight of 70g is 20000 is blocked under strong stirring
It crosses dropping funel to be added drop-wise to dropwise in above-mentioned solution, reacts 20min at 40 DEG C, prepare prepolymer D, finally by 20g 4,4 '-
Di-2-ethylhexylphosphine oxide (2- ethyl 6- methyl cyclohexylamines) is dissolved in mixed solution, is added dropwise in reactor by dropping funel, 10 DEG C
Lower reaction 20min, product is poured into mold, and volatilization removal solvent, obtains elastomer at room temperature.
Mechanics Performance Testing is carried out to it, it is 3MPa, elongation at break 230% to draw high intensity.
The molecular weight for the dimethyl silicone polymer C that amine propyl blocks in this comparative example is excessive, makes phase point of the soft segment with hard section
Apparent from excessively, sharp microphase-separated makes the mechanical property of elastomer reduce.
Comparative example 4,
A kind of preparation method for the polyurea elastomer substituting polyethers completely with polysiloxanes, including steps are as follows:
In the four-hole boiling flask equipped with constant pressure funnel, drying tube, mechanical agitation and nitrogen access equipment, 20g is added
Methyl diphenylene diisocyanate, toluene and n-hexane (volume ratio 5 is used in combination:1) mixed solvent dissolving is complete, stirs strongly
It mixes down, the dimethyl silicone polymer C dissolvings that the amine propyl that the molecular weight of 60g is 5000 blocks is passed through into dropping funel later completely
It is added drop-wise to dropwise in above-mentioned solution, reacts 30min at 40 DEG C, prepare prepolymer D, it is molten that 20g ethylenediamines are finally dissolved in mixing
In liquid, it is added dropwise in reactor at 50 DEG C by dropping funel and reacts 10min, product is poured into mold, is volatilized at room temperature
Solvent is removed, elastomer is obtained.
Mechanics Performance Testing is carried out to it, it is 3MPa, elongation at break 300% to draw high intensity.
Since reaction temperature is excessively high when chain extending reaction in this comparative example, reaction can be caused excessively violent, product is precipitated in advance,
What reaction carried out is not thorough, and simultaneous reactions are not easy to control, and product mechanical property is relatively low.
Claims (10)
1. a kind of polyurea elastomer substituting polyethers completely with polysiloxanes, which is characterized in that the elastomer has shown in formula (I)
General formula:
Wherein n, m are the integer more than or equal to 1;
X isOr
CH2CH2CH2CH2CH2CH2;
Y is CH2CH2、CH2CH(CH3)CH2CH2CH2、CH2CH2CH2CH2CH2CH2Or
2. the polyurea elastomer according to claim 1 for substituting polyethers completely with polysiloxanes, which is characterized in that 1≤n≤
150,1≤m≤50.
3. the preparation method of the polyurea elastomer as claimed in claim 1 or 2 for substituting polyethers completely with polysiloxanes, including step
It is as follows:
(1) in the in the mixed solvent of organic solvent A and B, the dimethyl silicone polymer C and two isocyanides of amine propyl sealing end are separately added into
Ester compound is stirred to react 10-80min at 0-50 DEG C, generates the prepolymer D of isocyanate-terminated low molecular weight;
(2) the prepolymer D generated in step (1) is reacted into 10-500min at 0-30 DEG C with end amine compound, is contained
The mixed solution of polysiloxanes-polyurea polymer;Then volatilization removal solvent substitutes polyethers completely to get to polysiloxanes
Polyurea elastomer.
4. the preparation method of the polyurea elastomer according to claim 3 for substituting polyethers completely with polysiloxanes, feature
It is, the organic solvent A described in step (1) is dimethylbenzene, tetrahydrofuran, dimethyl sulfoxide (DMSO), toluene, acetone, hexamethylene or two
Six ring of oxygen;
The organic solvent B is ether, dichloromethane, ethyl acetate, isopropanol or n-hexane;
Organic solvent A, the volume ratio of B are (5-15):1.
5. the preparation method of the polyurea elastomer according to claim 3 for substituting polyethers completely with polysiloxanes, feature
It is, the dimethyl silicone polymer C of the amine propyl sealing end described in step (1) has general formula shown in formula (II):
In formula (II), the value of n is identical as formula (I);
The relative molecular weight ranging from 1000-10000g/mol of the dimethyl silicone polymer C of amine propyl sealing end.
6. the preparation method of the polyurea elastomer according to claim 3 for substituting polyethers completely with polysiloxanes, feature
It is, the diisocyanate cpd described in step (1) is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,5-
Naphthalene diisocyanate, hexamethylene diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methyl hydride diisocyanate,
Isophorone diisocyanate, paraphenylene diisocyanate, terephthalylidene diisocyanate or tetramethylxylene two
Isocyanates.
7. the preparation method of the polyurea elastomer according to claim 3 for substituting polyethers completely with polysiloxanes, feature
It is, isocyanide in the Amino End Group and diisocyanate cpd of the dimethyl silicone polymer C of the amine propyl sealing end described in step (1)
The molar ratio of perester radical is 1:(2-15), preferably 1:(3-8).
8. the preparation method of the polyurea elastomer according to claim 3 for substituting polyethers completely with polysiloxanes, feature
It is, reaction temperature is 5-40 DEG C in step (1), reaction time 10-50min.
9. the preparation method of the polyurea elastomer according to claim 3 for substituting polyethers completely with polysiloxanes, feature
It is, the end amine compound described in step (2) is ethylenediamine, hexamethylene diamine, bis- (p-aminobenzoic acid) propylene glycol esters, 1,2- bis-
(2- aminophenyls are thio) ethane, 2- methyl-1s, 5- pentanediamines, 3,5- diamino -4- trifluoromethyls phenetole or 4,4 '-methylenes
Base is bis- (2- ethyl 6- methyl cyclohexylamines).
10. the preparation method of the polyurea elastomer according to claim 3 for substituting polyethers completely with polysiloxanes, feature
It is, the reaction temperature described in step (2) is 0-15 DEG C, reaction time 5-20min;
Preferably, the time of step (2) solvent flashing at room temperature, solvent flashing is 2-48h.
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CN112457468A (en) * | 2020-12-23 | 2021-03-09 | 中国科学院青岛生物能源与过程研究所 | High-elasticity polydimethylsiloxane polymer and application thereof |
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WO2022200330A1 (en) | 2021-03-22 | 2022-09-29 | Norwegian University Of Science And Technology (Ntnu) | Polymer with improved fracture toughness |
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CN115819711A (en) * | 2022-11-24 | 2023-03-21 | 四川大学 | Reactive extrusion 3D printing silicone rubber-polyurea material and application thereof |
CN116082644A (en) * | 2023-01-10 | 2023-05-09 | 粤芯半导体技术股份有限公司 | Organic silicon elastomer and preparation method thereof, flexible sensor and preparation method thereof |
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WO2022200330A1 (en) | 2021-03-22 | 2022-09-29 | Norwegian University Of Science And Technology (Ntnu) | Polymer with improved fracture toughness |
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CN115521436A (en) * | 2022-09-08 | 2022-12-27 | 盛鼎高新材料有限公司 | High-weather-resistance polyurethane elastomer and processing technology thereof |
CN115521436B (en) * | 2022-09-08 | 2023-10-27 | 盛鼎高新材料有限公司 | Polyurethane elastomer with high weather resistance and processing technology thereof |
CN115819711A (en) * | 2022-11-24 | 2023-03-21 | 四川大学 | Reactive extrusion 3D printing silicone rubber-polyurea material and application thereof |
CN115819711B (en) * | 2022-11-24 | 2024-04-05 | 四川大学 | Reactive extrusion 3D printing silicone rubber-polyurea material and application thereof |
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CN116285618B (en) * | 2022-12-20 | 2023-11-07 | 蔚湃建筑科技(上海)有限公司 | Organosilicon waterproofing agent and preparation method thereof |
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