Modified polysiloxane and application thereof

Abstract

A modified polysiloxane has formula (I) ##STR00001##
In formula (I) m is an integer between 0 and 10000; n is an integer between 0 and 10000; m and n cannot be equal to 0 simultaneously; R.sub.1-R.sub.7 are the same or different; and at least one of R.sub.1-R.sub.7 includes a group having a reversible chemical bond system based on a hydrogen bond, a coordinate bond, or a covalent bond. The polysioxane is used as a main chain to introduce a reversible chemical bond having temperature sensitivity by using a chemical method, so as to obtain a polymer material which is highly sensitive to temperature. The temperature-sensitive properties of materials provide functional materials for specific applications, such as medical external fixation materials, orthopedic materials, and packaging materials, can be obtained by using particular processing and preparation methods.

Claims

1. A temperature-sensitive material, comprising a modified polysiloxane and one or more metal ions selected from alkali metal ions, alkaline earth metal ions, and transition metal ions, wherein the modified polysiloxane is of Formula I: ##STR00089## wherein m is an integer from 0 to 10000, n is an integer from 0 to 10000, with the proviso that m and n are not simultaneously 0; R.sub.1-R.sub.7 are the same or different, independently selected from a moiety of Formula II, an amino group, a hydroxyl group, a thiol group, a carboxyl group, a methoxyl group, a nitro group, a halogen atom, an unsubstituted C1-C50 alkyl group, an unsubstituted C1-C50 cycloalkyl group, a substituted C1-C50 alkyl group, and a substituted C1-C50 cycloalkyl group, wherein the substituents are selected from one or more amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups or halogen atoms, and a phenyl group or naphthyl group non-substituted or substituted by one or more C1-C50 alkyl groups, C1-C50 alkoxy groups, amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups, halogen atoms, with the proviso that at least one of R.sub.1-R.sub.7 is the moiety of Formula II; ##STR00090## in Formula II, a, b and c are the same or different, and represent units formed by connecting one or more of —CH.sub.2—, —NH—, —O—, —S—, —CO— and —CH(R.sub.8)— in any order; R.sub.8 is selected from a hydrogen atom, an amino group, a hydroxyl group, a thiol group, a carboxyl group, a methoxyl group, a nitro group, a halogen atom, an unsubstituted C1-C50 alkyl group, an unsubstituted C1-050 cycloalkyl group, a substituted C1-C50 alkyl group, and a substituted C1-C50 cycloalkyl group, wherein the substituents are selected from one or more amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups or halogen atoms, and a phenyl group or naphthyl group non-substituted or substituted by one or more C1-C50 alkyl groups, C1-C50 alkoxy groups, amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups, and halogen atoms; p.sub.1, p.sub.2 and p.sub.3 are the same or different, and are integers from 0 to 500; q is an integer from 0 to 500; L.sub.0 is selected from ##STR00091## X.sub.1 represents —CH.sub.2—, —NH—, —O—, —S—, —COO—, or —CO—; Y.sub.1 represents ##STR00092##

2. A temperature-sensitive material comprising a modified polysiloxane, ##STR00093## wherein m is an integer from 0 to 10000, n is an integer from 0 to 10000, with the proviso that m and n are not simultaneously 0; R.sub.1-R.sub.7 are the same or different, independently selected from a moiety of Formula II, an amino group, a hydroxyl group, a thiol group, a carboxyl group, a methoxyl group, a nitro group, a halogen atom, an unsubstituted C1-C50 alkyl group, an unsubstituted C1-C50 cycloalkyl group, a substituted C1-C50 alkyl group, and a substituted C1-C50 cycloalkyl group, wherein the substituents are selected from one or more amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups or halogen atoms, and a phenyl group or naphthyl group non-substituted or substituted by one or more C1-C50 alkyl groups, C1-C50 alkoxy groups, amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups, and halogen atoms, with the proviso that at least one among R.sub.1-R.sub.7 is the moiety of Formula II; ##STR00094## in Formula II, a, b, and c are the same or different, and represent units formed by connecting one or more of —CH.sub.2—, —NH—, —O—, —S—, —COO—, —CO—, and —CH(R.sub.8)— in any order; R.sub.8 is selected from a hydrogen atom, an amino group, a hydroxyl group, a thiol group, a carboxyl group, a methoxyl group, a nitro group, a halogen atom, a unsubstituted C1-C50 alkyl group, a unsubstituted C1-050 cycloalkyl group, a substituted C1-050 alkyl group, and a substituted C1-050 cycloalkyl group, wherein the substituents are selected from one or more amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups or halogen atoms, and a phenyl group or naphthyl group non-substituted or substituted by one or more C1-050 alkyl groups, C1-050 alkoxy groups, amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups, and halogen atoms; p.sub.1, p.sub.2 and p.sub.3 are the same or different, and are integers from 0 to 500; q is an integer from 0 to 500, wherein: L.sub.0 represents a group having a reversible chemical bond system based on a hydrogen bond, and is selected from: ##STR00095## or, L.sub.0 represents a group having a reversible chemical bond system based on a coordinate bond, and is formed by a ligand and metal ions M through coordination, and the ligand is selected from: ##STR00096## wherein X.sub.1 represents —CH.sub.2—, —NH—, —O—, —S—, —COO—, or —CO—; Y.sub.1 represents: ##STR00097## R.sub.9 is selected from a hydrogen atom or an amino group, a hydroxyl group, a thiol group, a carboxyl group, a methoxyl group, a nitro group, a halogen atom, a C1-C50 alkyl group or cycloalkyl group non-substituted or substituted by one or more amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups or halogen atoms, and a phenyl group or naphthyl group non-substituted or substituted by one or more C1-C50 alkyl groups, C1-C50 alkoxy groups, amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups, and halogen atoms; M is one or more of alkali metal, alkaline-earth metal, transition metal and rare earth metal ions; or, L.sub.0 represents a group having a reversible chemical bond system based on a covalent bond, and is selected from ##STR00098## X.sub.2 represents —NH—, —O—, —S—, —COO— or —CO—; and Y.sub.2 represents: ##STR00099##

3. A method for preparing a temperature sensitive material, comprising: mixing a modified polysiloxane and one or more additives to form a mixture; and extruding the mixture to obtain the temperature sensitive material, wherein the modified polysiloxane is of Formula I, ##STR00100## wherein m is an integer from 0 to 10000, n is an integer from 0 to 10000, with the proviso that m and n are not simultaneously 0; R.sub.1-R.sub.7 are the same or different, independently selected from a moiety of Formula II, an amino group, a hydroxyl group, a thiol group, a carboxyl group, a methoxyl group, a nitro group, a halogen atom, an unsubstituted C1-C50 alkyl group, an unsubstituted C1-C50 cycloalkyl group, a substituted C1-C50 alkyl group, and a substituted C1-C50 cycloalkyl group, wherein the substituents are selected from one or more amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups or halogen atoms, and a phenyl group or naphthyl group non-substituted or substituted by one or more C1-C50 alkyl groups, C1-C50 alkoxy groups, amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups, and halogen atoms, with the proviso that at least one among R.sub.1-R.sub.7 is the moiety of Formula II; ##STR00101## in Formula II, a, b, and c are the same or different, and represent units formed by connecting one or more of —CH.sub.2—, —NH—, —O—, —S—, —COO—, —CO—, and —CH(R.sub.8)— in any order; R.sub.8 is selected from a hydrogen atom, an amino group, a hydroxyl group, a thiol group, a carboxyl group, a methoxyl group, a nitro group, a halogen atom, an unsubstituted C1-C50 alkyl group, an unsubstituted C1-050 cycloalkyl group, a substituted C1-050 alkyl group, and a substituted C1-050 cycloalkyl group, wherein the substituents are selected from one or more amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups or halogen atoms, and a phenyl group or naphthyl group non-substituted or substituted by one or more C1-C50 alkyl groups, C1-050 alkoxy groups, amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups, and halogen atoms; p.sub.1, p.sub.2 and p.sub.3 are the same or different, and are integers from 0 to 500; q is an integer from 0 to 500, wherein: L.sub.0 represents a group having a reversible chemical bond system based on a hydrogen bond, and is selected from: ##STR00102## or, L.sub.0 represents a group having a reversible chemical bond system based on a coordinate bond, and is formed by a ligand and metal ions M through coordination, and the ligand is selected from: ##STR00103## wherein X.sub.1 represents —CH.sub.2—, —NH—, —O—, —S—, —COO—, or —CO—; Y.sub.1 represents: ##STR00104## R.sub.9 is selected from a hydrogen atom or an amino group, a hydroxyl group, a thiol group, a carboxyl group, a methoxyl group, a nitro group, a halogen atom, a C1-050 alkyl group or cycloalkyl group non-substituted or substituted by one or more amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups or halogen atoms, and a phenyl group or naphthyl group non-substituted or substituted by one or more C1-C50 alkyl groups, C1-050 alkoxy groups, amino groups, hydroxyl groups, thiol groups, carboxyl groups, methoxyl groups, nitro groups, and halogen atoms; M is one or more of alkali metal, alkaline-earth metal, transition metal and rare earth metal ions; or, L.sub.0 represents a group having a reversible chemical bond system based on a covalent bond, and is selected from ##STR00105## X.sub.2 represents —NH—, —O—, —S—, —COO— or —CO—; and Y.sub.2 represents: ##STR00106##

4. The method according to claim 3, wherein each of the one or more additives is selected from a polymer additive, a plasticizer, a toughening agent, a stabilizing agent, a lubricating agent, a nanometer additive, a filler, a color additive, and a medicinal component.

5. A method for preparing the temperature sensitive material of claim 1, comprising: mixing the modified polysiloxane, the one or more metal ions, and one or more additives to form a mixture; and extruding the mixture to obtain the temperature sensitive material.

6. The method according to claim 5, wherein each of the one or more additives is selected from a polymer additive, a plasticizer, a toughening agent, a stabilizing agent, a lubricating agent, a nanometer additive, a filler, a color additive, and a medicinal component.

7. The temperature-sensitive material of claim 2, wherein, in Formula I, m is an integer from 0 to 200, n is an integer from 0 to 200; R.sub.1-R.sub.7 are selected from the moiety of Formula II, an amino group, a hydroxyl group, a thiol group, a carboxyl group, a methoxyl group, a nitro group, a phenyl group, a benzyl group, a phenolic group, an alkoxyphenyl group, a C1-C30 alkyl group, a C1-C30 alkoxy group, and a C1-C30 halogenated alkyl group, with the proviso that at least one among R.sub.1-R.sub.7 is the moiety of Formula II.

8. The temperature-sensitive material of claim 2, wherein, in Formula II, a, b and c are the same or different, and represent units formed by connecting one or more of —CH.sub.2—, —NH—, —O—, —CO—, and —CH(R.sub.8)— in any order, and R.sub.8 represents a methyl group, an ethyl group, a phenyl group, a hydroxyl group, a thiol group, a carboxyl group, and an amino group; p.sub.1, p.sub.2, and p.sub.3 are integers from 1 to 20; and q is an integer from 0 to 20.

9. The temperature-sensitive material of claim 8, wherein, in Formula II, p.sub.2 and p.sub.3 are 0, -[(a)p.sub.1-(b)p.sub.2-(c)p.sub.3]q- represents —(CH.sub.2)p.sub.1-, —(NH)p.sub.1-, —(S)p.sub.1-, —(CO)p.sub.1-, or —(CH(R.sub.8))p.sub.1-, p.sub.1 is an integer from 1 to 20, and q is 1; or p.sub.3 is equal to 0, -[(a)p.sub.1-(b)p.sub.2-(c)p.sub.3]q- represents —[(CH.sub.2)p.sub.1-(NH)p.sub.2]q-, —[(CH.sub.2)p.sub.1-(O)p.sub.2]q-, —[(CH.sub.2)p.sub.1-(S)p.sub.2]q-, —[CH.sub.2)p.sub.1-(COO)p.sub.2]q-, —[(CH.sub.2)p.sub.1-(CO)p.sub.2]q-, —[(CH(R.sub.8))p.sub.1-(CH.sub.2)p.sub.2]-, —[(NH)p.sub.1-(CH.sub.2)p.sub.2]q-, —[(S)p.sub.1-(CO)p.sub.2]- and —[(CH(R.sub.8))p.sub.1-(COO)p.sub.2]q-, p.sub.1 and p.sub.2 are integers from 1 to 20, and q is an integer from 1 to 20; or -[(a)p.sub.1-(b)p.sub.2-(c)p.sub.3]q- represents —[(CH.sub.2)p.sub.1-(O)p.sub.2-(CH.sub.2)p.sub.3]q-, -[(CH.sub.2)p.sub.1-(CH.sub.2)p.sub.2-(O)p.sub.3]q-, -[(CO)p.sub.1-(CH.sub.2)p.sub.2-(CO)p.sub.3]q, -[(CO)p.sub.1-(O)p.sub.2-(CO)p.sub.3-]q, -[(CH(R.sub.8))p.sub.1-(CH.sub.2)p.sub.2-(CH(R.sub.8))p.sub.3]q-, or —[(CH(R.sub.8))p.sub.1-(CH.sub.2)p.sub.2-(CH.sub.2) p.sub.3]q-, p.sub.1, p.sub.2 and p.sub.3 are integers from 1 to and 20, and q is an integer from 1 to 20; and R.sub.8 represents a methyl group, an ethyl group, a phenyl group, a hydroxyl group, a carboxyl group, or an amino group.

10. The temperature-sensitive material of claim 2, wherein, in Formula II, L.sub.0 represents ##STR00107## ##STR00108##

11. The temperature-sensitive material of claim 1, wherein the one or more metal ions is selected from Zn.sup.2+, Cu.sup.2+, Fe.sup.3+, Fe.sup.2+, Co.sup.2+, Pb.sup.2+, Sn.sup.2+, Al.sup.3+, Ag.sup.+, Ni.sup.2+, Ca.sup.2+, Eu.sup.3+, Tb.sup.3+, Na.sup.+, and Kt.sup.+.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a temperature sensitivity characterization curve of a material obtained in Embodiment 1.

(2) FIG. 2 is a mechanical property (stress-strain) curve of a material obtained in Embodiment 1.

DETAILED DESCRIPTION

(3) Now, a structure, a preparation method and a mechanism of a temperature-sensitive polymer material involved in the present invention and application thereof in a fast shaping external fixation support frame are further illustrated in conjunction with embodiments.

Embodiment 1 Temperature-Sensitive Polymer Material Based on Hydrogen Bond

(4) Step 1: 150 g of anhydrous toluene was added into a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening. 72 g of allyl glycidyl ether (0.63 mol) was added with stirring. Then, 37.5 g of polyalkylhydrosiloxane with a hydrogen content of 1.6 wt % (M.sub.n was about 3000, R.sub.1-R.sub.6 were methyl groups, m equals to 0, and n has a value in the range of 40 to 55, 0.6 mol per mol of Si—H) was added into a mixed reaction system of toluene and allyl glycidyl ether. Then, 20 mg of a Karstedt platinum catalyst (20 wt % Pt) was added dropwise into the mixed reaction system. After dropping, the temperature was controlled to be 50° C., and the reaction was continuously performed for 12 h. After the reaction was completed, reduced pressure distillation was adopted to obtain 105.5 g of polysiloxane functionalized with allyl glycidyl ether with a yield of 97.2%. Through .sup.1H NMR characterization, the silicon hydrogen addition rate was 98.5%. The equation is as follows:

(5) ##STR00058##

(6) Step 2: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 105.5 g of polysiloxane functionalized with allyl glycidyl ether obtained in Step 1 was dissolved into 150 mL of tetrahydrofuran. 100 mL of 25 wt % ammonium hydroxide solution was added into the system with stirring. The reaction temperature was controlled to be 50° C. The reaction was continuously performed for 12 h. After the reaction was completed, a tetrahydrofuran phase was extracted out. 100 mL of water was added into the extracted tetrahydrofuran to further purify the product. Anhydrous sodium sulfate was added for drying. Through reduced pressure distillation, 106.9 g of a final product of polysiloxane functionalized with amino group-hydroxyl group was obtained with a yield of 96.5%. The equation is as follows:

(7) ##STR00059##

(8) Upon the change of temperature, the hydrogen bond in the structure of the above polysiloxane functionalized with amino group-hydroxyl group changes as follows:

(9) ##STR00060##

(10) Dotted lines represent possibly existing hydrogen bond interaction in the polymer material. A group T has the following structural formula:

(11) ##STR00061##

(12) Temperature-Sensitive Property Characterization:

(13) In order to illustrate the temperature-sensitive properties of the material, a temperature-sensitive index η of the material is defined as a change value of a corresponding mechanical strength (energy storage modulus) when the temperature rose from 20° C. to 120° C. (or a corresponding temperature lowering process) (η=G′(120)/G′(20)). The temperature-sensitivity curve is shown in FIG. 1. Specific parameters are shown in Table 1.

(14) Mechanical Property Characterization:

(15) In order to illustrate the mechanical property of the temperature-sensitive material, a variable-temperature static stretching experiment was performed on the temperature-sensitive material to obtain a stress-strain curve. Through calculation, the Young modulus, the maximum stress and the maximum strain value of the material at a room temperature (25° C.) were obtained. For the product obtained in Embodiment 1, the mechanical property curve is shown in FIG. 2. Specific parameters are shown in Table 1.

(16) The temperature-sensitive polymer material obtained in the present embodiment has a temperature-sensitive coefficient G′(120)/G′(20) of 16000, the Young modulus of 520 MPa, the maximum stress of 5.9 MPa, and the maximum strain of 5.4%. The above parameters show that the material has excellent temperature-sensitive coefficient, and also has good mechanical properties at the same time.

Embodiment 2 Temperature-Sensitive Polymer Material Based on Hydrogen Bond

(17) Step 1: 150 g of anhydrous toluene was added into a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening. 72 g of methyl methacrylate (0.72 mol) was added with stirring. Then, 75 g of polyalkylhydrosiloxane with a hydrogen content of 0.8 wt % (M.sub.n was about 4000, R.sub.1-R.sub.6 were methyl groups, m/n was 1/1, m has a value in the range of 30 to 40, and n has a value in the range of 30 to 40, 0.6 mol per mol of Si—H) was added into a mixed reaction system of toluene and methyl methacrylate. Then, 20 mg of a Karstedt platinum catalyst (20 wt % Pt) was added dropwise into the mixed reaction system. After dropping, the temperature was controlled to be 50° C., and the reaction was continuously performed for 12 h. After the reaction was completed, reduced pressure distillation was adopted to obtain 131.5 g of polysiloxane functionalized with methyl methacrylate with a yield of 97.2%. Through .sup.1H NMR characterization, the silicon hydrogen addition rate was 97.5%. The equation is as follows:

(18) ##STR00062##

(19) Step 2: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 131.5 g of polysiloxane functionalized with methyl methacrylate obtained in Step 1 was dissolved into 150 mL of tetrahydrofuran. 100 mL of 80 wt % hydrazine hydrate solution was added into the system with stirring. The reaction temperature was controlled to be 50° C. The reaction was continuously performed for 12 h. After the reaction was completed, a tetrahydrofuran phase was extracted out. 100 mL of water was added into the extracted tetrahydrofuran to further purify the product. Through reduced pressure distillation, 118.5 g of a final product of polysiloxane functionalized with hydrazide was obtained with a yield of 95.6%. The equation is as follows:

(20) ##STR00063##

(21) Upon the change of the temperature, the hydrogen bond in the structure of the above polysiloxane functionalized with hydrazide changes as follows:

(22) ##STR00064##

(23) Dotted lines represent possibly existing hydrogen bond interaction in the polymer material. A group T has the following structural formula:

(24) ##STR00065##

(25) The temperature-sensitive property and mechanical property characterization of the product of the polysiloxane functionalized with reversible hydrogen bonds obtained in the present embodiment is similar to the properties of the product prepared in Embodiment 1. Detailed data is shown in Table 1. The temperature-sensitive polymer material obtained in the present embodiment has a temperature-sensitive coefficient G′(120)/G′(20) of 12000, the Young modulus of 610 MPa, the maximum stress of 6.2 MPa, and the maximum strain of 12.5%. The above parameters show that the material has excellent temperature-sensitive coefficient, and also has good mechanical properties at the same time.

Embodiment 3 Temperature-Sensitive Polymer Material Based on Hydrogen Bond

(26) Step 1: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 131.5 g of polysiloxane functionalized with methyl methacrylate obtained in Step 1 of Embodiment 2 was dissolved into 150 mL of tetrahydrofuran, and 36 g of lithium aluminum hydride was added into the system with stirring. The reaction temperature was controlled to be 25° C. The reaction was continuously performed for 12 h. After the reaction was completed, an organic phase was collected through filtration. Then, through reduced pressure distillation, the solvent was removed to obtain 112.3 g of a final product of polysiloxane functionalized with hydroxyl group with a yield of 93.8%. The equation is as follows:

(27) ##STR00066##

(28) Upon the change of the temperature, the hydrogen bond in the structure of the above polysiloxane functionalized with hydroxyl group changes as follows:

(29) ##STR00067##

(30) Dotted lines represent possibly existing hydrogen bond interaction in the polymer material. A group T has the following structural formula:

(31) ##STR00068##

(32) The temperature-sensitive property and mechanical property characterization of the product of the polysiloxane functionalized with reversible hydrogen bonds obtained in the present embodiment is similar to the properties of the product prepared in Embodiment 1. Detailed data is shown in Table 1. The temperature-sensitive polymer material obtained in the present embodiment has a temperature-sensitive coefficient G′(120)/G′(20) of 9000, the Young modulus of 380 MPa, the maximum stress of 4.6 MPa, and the maximum strain of 25.3%. The above parameters show that the material has excellent temperature-sensitive coefficient, and also has good mechanical properties at the same time.

(33) Synthesis methods of other temperature-sensitive polymer materials based on a hydrogen bond are similar to those in Embodiment 1, Embodiment 2 and Embodiment 3, and only reaction raw materials need to be correspondingly replaced.

Embodiment 4 Temperature-Sensitive Polymer Material Based on Coordination Bond

(34) Step 1: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 85 g (about 0.5 mol) of a product of polysiloxane functionalized with hydrazide obtained in Embodiment 2 (M.sub.n was about 6000, R.sub.1-R.sub.6 were methyl groups, m/n was 1/1, m has a value in the range of 30 to 40, and n has a value in the range of 30 to 40) was dissolved in tetrahydrofuran. 54 g (about 0.5 mol) of 2-pyridinecarboxaldehyde was dissolved in tetrahydrofuran. Solutions of two reactants were slowly mixed and stirred. The reaction temperature was controlled to be 50° C. The reaction was continuously performed for 12 h. After the reaction was completed, the tetrahydrofuran was removed through reduced pressure distillation to obtain 130.5 g of an intermediate product of polysiloxane functionalized with pyridine with a yield of 94.8%. The equation is as follows:

(35) ##STR00069##

(36) Step 2: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 130.5 g (about 0.5 mol) of the product of polysiloxane functionalized with pyridine obtained in Step 1 was dissolved in tetrahydrofuran. 125 mL of 2 mol/L CuCl.sub.2 methanol solution was slowly added into the tetrahydrofuran solution with stirring. A reaction temperature was controlled to be 25° C. The reaction was continuously performed for 12 h. After the reaction was completed, the tetrahydrofuran and methanol were removed through reduced pressure distillation to obtain 158.3 g of polysiloxane based on a Cu(II)-pyridine imine coordination group with a yield of 96.8%. The equation is as follows:

(37) ##STR00070##

(38) The change of the coordination bond under the change of temperature is as follows:

(39) ##STR00071##

(40) Association and dissociation processes of the coordination bond could be regulated through temperature control. A group T has the following structural formula:

(41) ##STR00072##

(42) The temperature-sensitive property and mechanical property characterization of the product of the polysiloxane functionalized with reversible coordination bonds obtained in the present embodiment is similar to the properties of the product prepared in Embodiment 1. Detailed data is shown in Table 1. The temperature-sensitive polymer material obtained in the present embodiment has a temperature-sensitive coefficient G′(120)/G′(20) of 20000, the Young modulus of 710 MPa, the maximum stress of 7.3 MPa, and the maximum strain of 7.4%. The above parameters show that the material has excellent temperature-sensitive coefficient, and also has good mechanical properties at the same time.

Embodiment 5 Temperature-Sensitive Polymer Material Based on Coordination Bond

(43) Step 1: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 105.5 g of polysiloxane functionalized with allyl glycidyl ether synthesized in Step 1 of Embodiment 1 was dissolved in 150 mL of tetrahydrofuran. 40 g (about 0.6 mol) of imidazole was dissolved in 100 mL of tetrahydrofuran. The tetrahydrofuran solution of the imidazole was added into the polysiloxane solution with stirring. The reaction temperature was controlled to be 80° C. The reaction was continuously performed for 12 h. After the reaction was completed, the solution was concentrated to ¼ of the original volume. Then, 300 mL of methanol was added into the reaction system. A standing and layering was performed for separation. Precipitates were collected. Through reduced pressure distillation, the solvent was removed to obtain 128.6 g of a final product of polysiloxane functionalized with imidazolyl group with a yield of 95.7%. The equation is as follows:

(44) ##STR00073##

(45) Step 2: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 128.6 g (about 0.6 mol) of the product of polysiloxane functionalized with imidazolyl group obtained in Step 1 was dissolved in tetrahydrofuran. 150 mL of 2 mol/L ZnCl.sub.2 methanol solution was slowly added into the tetrahydrofuran solution with stirring. The reaction temperature was controlled to be 50° C. The reaction was continuously performed for 8 h. After the reaction was completed, the tetrahydrofuran and methanol were removed through reduced pressure distillation to obtain 154.3 g of polysiloxane based on a Zn(II)-imine coordination group with a yield of 95.8%. The equation is as follows:

(46) ##STR00074##

(47) The chance of the coordination bond upon changing temperature is as follows:

(48) ##STR00075##

(49) Association and dissociation processes of the coordination bond could be regulated through temperature control. A group T has the following structural formula:

(50) ##STR00076##

(51) The temperature-sensitive property and mechanical property characterization of the product of the polysiloxane functionalized with reversible coordination bonds obtained in the present embodiment is similar to the properties of the product prepared in Embodiment 1. Detailed data is shown in Table 1. The temperature-sensitive polymer material obtained in the present embodiment has a temperature-sensitive coefficient G′(120)/G′(20) of 19000, the Young modulus of 570 MPa, the maximum stress of 7.3 MPa, and the maximum strain of 6.5%. The above parameters show that the material has excellent temperature-sensitive coefficient, and also has good mechanical properties at the same time.

Embodiment 6 Temperature-Sensitive Polymer Material Based on Coordination Bond

(52) Step 1: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 131.5 g of polysiloxane functionalized with methyl methacrylate synthesized in Step 1 of Embodiment 2 was dissolved in 150 mL of tetrahydrofuran. 300 mL of 1 wt % hydrochloric acid solution was added with stirring. The reaction temperature was controlled to be 60° C. The reaction was continuously performed for 12 h. After the reaction was completed, a standing and layering was performed for separation. A tetrahydrofuran phase was extracted. The solvent was removed through reduced pressure distillation to obtain 118.6 g of a final product of polysiloxane functionalized with carboxyl group with a yield of 96.1%. The equation is as follows:

(53) ##STR00077##

(54) Step 2: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 118.6 g (about 0.6 mol) of the product of polysiloxane functionalized with carboxyl group obtained in Step 1 was dissolved in tetrahydrofuran. 150 mL of 2 mol/L ZnCl.sub.2 methanol solution and 60.6 g of triethylamine were slowly added into the tetrahydrofuran solution with stirring. The reaction temperature was controlled to be 50° C. The reaction was continuously performed for 12 h. After the reaction was completed, the tetrahydrofuran, the methanol and the excessive triethylamine were removed through reduced pressure distillation to obtain 154.3 g of polysiloxane based on a Zn(II)-carboxyl coordinate group with a yield of 94.9%. The equation is as follows:

(55) ##STR00078##

(56) The change of coordination bond upon changing the temperature is as follows:

(57) ##STR00079##

(58) Association and dissociation processes of the coordination bond could be regulated through temperature control. A group T has the following structural formula:

(59) ##STR00080##

(60) The temperature-sensitive property and mechanical property characterization of the product of the polysiloxane functionalized with reversible coordination bond obtained in the present embodiment is similar to the properties of the product prepared in Embodiment 1. Detailed data is shown in Table 1. The temperature-sensitive polymer material obtained in the present embodiment has a temperature-sensitive coefficient G′(120)/G′(20) of 17000, the Young modulus of 680 MPa, the maximum stress of 8.6 MPa, and the maximum strain of 5.8%. The above parameters show that the material has excellent temperature-sensitive coefficient, and also has good mechanical properties at the same time.

(61) Synthesis methods of other temperature-sensitive polymer materials based on coordination bonds are similar to those in Embodiment 4, Embodiment 5 and Embodiment 6, and only reaction raw materials need to be correspondingly replaced.

Embodiment 7 Temperature-Sensitive Polymer Material Based on Covalent Bonds

(62) Step 1: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 105.5 g of polysiloxane functionalized with allyl glycidyl ether synthesized in Step 1 of Embodiment 1 was dissolved in 150 mL of tetrahydrofuran. 75.6 g (about 0.6 mol) of 2-furylacetic acid was dissolved in 100 mL of tetrahydrofuran. The tetrahydrofuran solution of 2-furylacetic acid was added into the polysiloxane solution with stirring. The reaction temperature was controlled to be 100° C. The reaction was continuously performed for 12 h. After the reaction was completed, the solution was concentrated to ¼ of the original volume. Then, 300 mL of methanol was added into the reaction system. A standing and layering process was performed for separation. Precipitates were collected. The solvent was removed through reduced pressure distillation to obtain 158.6 g of a final product of polysiloxane functionalized with furyl group with a yield of 96.7%. The equation is as follows:

(63) ##STR00081##

(64) Step 2: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 105.5 g of polysiloxane functionalized with allyl glycidyl ether synthesized in Step 1 of Embodiment 1 was dissolved in 150 mL of tetrahydrofuran. 75.6 g (about 0.6 mol) of 2-furylacetic acid was dissolved in 100 mL of tetrahydrofuran. 58.2 g (0.6 mol) of tetrahydrofuran solution of maleimide was added into the polysiloxane solution with stirring. The reaction temperature was controlled at 100° C. The reaction was continuously performed for 12 h. After the reaction was completed, the solution was concentrated to ¼ of the original volume. Then, 300 mL of methanol was added into the reaction system. A standing and layering process was performed for separation. Precipitates were collected. The solvent was removed through reduced pressure distillation to obtain 128.6 g of a final product of polysiloxane functionalized with maleimide group with a yield of 96.7%. The equation is as follows:

(65) ##STR00082##

(66) Step 3: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 158.6 g of polysiloxane functionalized with furyl group synthesized in Step 1 and 128.6 g of polysiloxane functionalized with maleimide group were dissolved in 150 mL of tetrahydrofuran. The above solutions were mixed and stirred. The solved was removed through reduced pressure distillation so that reactants were uniformly mixed. Then, the mixture was put into a polytetrafluoroethylene mold to be put into a 130° C. oven for reaction for 12 h. 280.2 g of a temperature-sensitive material based on a covalent bond was obtained with a yield of 98.7%. The equations is as follows:

(67) ##STR00083##

(68) The change of reversible covalent bond upon changing the temperature is as follows:

(69) ##STR00084##

(70) Crosslinking and decrosslinking effects of the covalent bond could be regulated through temperature control. A group T has the following structural formula:

(71) ##STR00085##

(72) The temperature-sensitive property and mechanical property characterization of the product of the polysiloxane functionalized with reversible covalent bond obtained in the present embodiment is similar to the properties of the product prepared in Embodiment 1. Detailed data is shown in Table 1. The temperature-sensitive polymer material obtained in the present embodiment has a temperature-sensitive coefficient G′(120)/G′(20) of 26000, the Young modulus of 890 MPa, the maximum stress of 12.7 MPa, and the maximum strain of 18.9%. The above parameters show that the material has excellent temperature-sensitive coefficient, and also has good mechanical properties at the same time.

Embodiment 8 Temperature-Sensitive Polymer Material Based on Covalent Bonds

(73) Step 1: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 105.5 g of polysiloxane functionalized with allyl glycidyl ether synthesized in Step 1 of Embodiment 1 was dissolved in 150 mL of tetrahydrofuran. 73.2 g (about 0.6 mol) of salicylaldehyde was dissolved in 200 mL of tetrahydrofuran. The tetrahydrofuran solution of salicylaldehyde was added into the polysiloxane solution with stirring. The reaction temperature was controlled at 100° C. The reaction was continuously performed for 12 h. After the reaction was completed, the solution was concentrated to ¼ of the original volume. Then, 300 mL of methanol was added into the reaction system. A standing and layering process was performed for separation. Precipitates were collected. The solvent was removed through reduced pressure distillation to obtain 161.6 g of a final product of polysiloxane functionalized with formyl group with a yield of 95.2%. The equation is as follows:

(74) ##STR00086##

(75) Step 2: In a dry four-neck flask with a temperature indicator, a condenser, a dropping funnel and an Ar introducing opening, 118.5 g of polysiloxane functionalized with hydrazide synthesized in Step 2 of Embodiment 2 was dissolved in 150 mL of tetrahydrofuran. 161.6 g of polysiloxane functionalized with formyl group in Step 1 of the present embodiment was dissolved in 200 mL of tetrahydrofuran. The two above tetrahydrofuran solutions were mixed with stirring. The reaction temperature was controlled at 80° C. The reaction was continuously performed for 12 h. After the reaction was completed, the solution was concentrated to ¼ of the original volume. Then, 300 mL of methanol was added into the reaction system. A standing and layering process was performed for separation. The solvent was removed through reduced pressure distillation to obtain 161.6 g of a final product of polysiloxane functionalized with formyl group with a yield of 95.2%. The equation is as follows:

(76) ##STR00087##

(77) The change of reversible covalent bond upon changing the temperature is as follows:

(78) ##STR00088##

(79) The temperature-sensitivepropertyandmechanicalpropertycharacterizationoftheproductofthe polysiloxane functionalized with reversible covalent bond obtained in the present embodiment is similar to the properties of the product prepared in Embodiment 1. Detailed data is shown in Table 1. The temperature-sensitive polymer material obtained in the present embodiment has a temperature-sensitive coefficient G′(120)/G′(20) of 13000, the Young modulus of 550 MPa, the maximum stress of 9.6 MPa, and the maximum strain of 53.9%. The above parameters show that the material has excellent temperature-sensitive coefficient, and also has good mechanical properties at the same time. Synthesis methods of other temperature-sensitive polymer materials based on a covalent bond are similar to those in Embodiment 7 and Embodiment 8, and only reaction raw materials need to be correspondingly replaced.

(80) TABLE-US-00001 TABLE 1 Temperature-sensitive property and mechanical property data of temperature-sensitive polymer obtained in Embodiments 1-8 Temperature-sensitive Young Maximum Maximum coefficient modulus stress strain Embodiment (G′(120)/G′(20)) (MPa) (MPa) (%) 1 16000 520 5.9 5.4 2 12000 610 6.2 12.5 3 9000 380 4.6 25.3 4 20000 710 7.3 7.4 5 19000 570 7.3 6.5 6 17000 680 8.6 5.8 7 26000 890 12.7 18.9 8 13000 550 9.6 53.9

Embodiment 9 Preparation of Fast Shaping Support Frame

(81) A formula is as follows (weight parts): 80 parts of temperature-sensitive polymers based on a coordinate bond in Embodiment 1; 5 parts of ethylene-vinyl acetate copolymers (additive); 5 parts of ethylene-octene copolymers (toughening agent); 5 parts of carbon fiber (filler); and 5 parts of titanium dioxide (pigment).

(82) A preparation method is as follows:

(83) a. Various ingredients were fed into a blending apparatus to be blended according to weight percent, so as to become a uniform blended material.

(84) b. The blended material was extruded.

(85) c. The extruded material was made to present a required shape through 3D printing, cutting, injection molding or calendaring according to requirements.

(86) Property indexes are as follows: strength temperature sensitivity δ=G.sub.max/G.sub.min(ΔT=100° C.)≥1000, the maximum stress≥5 MPa, the Young modulus≥500 MPa, a softening point is between 50 and 70° C., a deformation-fixation time≤10 min, an elongation at break≥5%, and a residual deformation rate≤10%.

(87) Preparation methods of the fast shaping external fixation support frames based on the temperature-sensitive polymers in Embodiments 2-8 are similar to that in Embodiment 9, and only temperature-sensitive polymers and auxiliary agents need to be correspondingly regulated.