Polyepoxybutane carbonate polyol, preparation method and application thereof, adhesive, and preparation method and application of adhesive

Abstract

The invention relates to the field of polyester, and discloses a polyepoxybutane carbonate polyol and a preparation method and application thereof, an adhesive and a preparation method and application thereof, the viscosity of the polyol at 25 DEG C is 200-5000 mPa.s, the carbon dioxide fixing amount is 10-30%, and the molecular weight distribution is 1.0-1.3. The polyepoxybutane carbonate polyol provided by the invention is relatively high in carbon dioxide fixing amount, relatively low in viscosity, and good in water resistance and weather resistance. The adhesive prepared from the polyepoxybutane carbonate polyol provided by the invention has excellent bonding strength and durability.

Description

Technical Field

[0001] This invention relates to the field of polyester, and more specifically to a polyepoxybutane carbonate polyol, its preparation method and application, as well as an adhesive, its preparation method and application. Background Technology

[0002] Hydrophobic polyols can improve the moisture resistance and hydrolytic stability of polyurethane materials. For example, polybutadiene polyols with an alkane main chain can be used to prepare polyurethane sealants. However, polybutadiene polyols have high viscosity at room temperature, making them difficult to handle and apply, and they are not resistant to ultraviolet light, which limits their application range.

[0003] Polyether carbonate polyols prepared using carbon dioxide and epoxy compounds have been widely reported, such as CN117402344A and CN104177805A, with commonly used monomers including propylene oxide and cyclohexane oxide. The addition of carbon dioxide gives the polymer both the stability of polyethers and the good mechanical properties of polyesters. However, as the amount of carbon dioxide fixed in the polymer increases, the viscosity gradually increases, affecting the application of polyether carbonate polyols.

[0004] Therefore, developing polyether carbonate polyols with excellent mechanical properties, strong water resistance and stability, as well as high carbon dioxide fixation and low viscosity is a technical challenge in this field. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem of high viscosity in polyether carbonate polyols in the prior art, and to provide a method for preparing polyepoxybutane carbonate polyols and their applications. The method for preparing polyepoxybutane carbonate polyols provided by this invention yields polymers with high carbon dioxide copolymerization rate, low viscosity, good water resistance, weather resistance, and excellent mechanical properties, making them particularly suitable for use in the preparation of adhesives.

[0006] To achieve the above objectives, the present invention provides a polyepoxybutane carbonate polyol having a viscosity of 200-5000 mPa·s at 25°C, a carbon dioxide fixation of 10-30%, and a molecular weight distribution of 1.0-1.3.

[0007] A second aspect of the present invention provides a method for preparing polyepoxybutane carbonate polyol, the method comprising: copolymerizing epoxybutane and carbon dioxide in the presence of a catalyst and an initiator.

[0008] A third aspect of the present invention provides a polyepoxybutane carbonate polyol obtained by the preparation method described herein.

[0009] The fourth aspect of this invention provides the application of the polyepoxybutane carbonate polyol described herein in the preparation of adhesives, coatings, sealants, and elastomers.

[0010] A fifth aspect of the present invention provides an adhesive prepared by reacting raw materials comprising the polyepoxybutane carbonate polyol described in the present invention and a curing agent.

[0011] The sixth aspect of the present invention provides a method for preparing an adhesive, the method comprising: mixing the polyepoxybutane carbonate polyol of the present invention with a curing agent, a second polyol, a chain extender and a catalyst, and then curing.

[0012] The seventh aspect of the present invention provides an adhesive prepared by the preparation method described herein.

[0013] The eighth aspect of the present invention provides the application of the adhesive described herein in the fields of construction, automobiles, and aerospace.

[0014] The polyepoxybutane carbonate polyol provided by this invention exhibits low viscosity and a narrow molecular weight distribution under high carbon dioxide fixation conditions, resulting in good water resistance and weather resistance. Adhesives prepared using the polyepoxybutane carbonate polyol provided by this invention demonstrate excellent adhesive strength and durability. Attached Figure Description

[0015] Figure 1 This is the 1H NMR spectrum of the product obtained in Preparation Example 1;

[0016] Figure 2 This is the 1H NMR spectrum of the product obtained in Preparation Example 3. Detailed Implementation

[0017] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0018] This invention provides a polyepoxybutane carbonate polyol with a viscosity of 200-5000 mPa·s at 25°C, a carbon dioxide fixation of 10-30%, and a molecular weight distribution of 1.0-1.3. The polyepoxybutane carbonate polyol provided by this invention exhibits low viscosity and a narrow molecular weight distribution under conditions of high carbon dioxide fixation, and demonstrates good water resistance and weather resistance.

[0019] According to a preferred embodiment of the present invention, the polyepoxybutane carbonate polyol has a viscosity of 400-2000 mPa·s at 25°C, preferably 800-1000 mPa·s.

[0020] According to a preferred embodiment of the present invention, the carbon dioxide fixation amount is 20-30%, preferably 20-25%.

[0021] According to a preferred embodiment of the present invention, the number average molecular weight is 200-6000, preferably 400-4000, and more preferably 3400-3800.

[0022] According to a preferred embodiment of the present invention, the molecular weight distribution is 1.0-1.25.

[0023] The aforementioned preferred polyepoxybutane carbonate polyol has low viscosity and narrow molecular weight distribution, and exhibits good water resistance and weather resistance.

[0024] As those skilled in the art will know in this invention, one end of the polyepoxybutane carbonate polyol contains an initiator structural unit. The initiator structural unit has no effect on the physicochemical parameters of the polyepoxybutane carbonate polyol. In this invention, the initiator segment is located at the end group, which will not be described in detail here.

[0025] In this invention, the polyepoxybutane carbonate polyol is a polymer obtained by copolymerizing epoxybutane and carbon dioxide in the presence of an initiator.

[0026] According to a preferred embodiment of the present invention, the poly(epoxybutane carbonate) polyol comprises epoxybutane structural unit A and / or epoxybutane structural unit B, preferably comprising epoxybutane structural unit A and epoxybutane structural unit B, wherein the weight ratio of the two is 0.1-10:1, preferably 0.5-2:1;

[0027] The structural formula of epoxide structural unit A is:

[0028] The structural formula of unit B of the epoxide butane mechanism is:

[0029] In this invention, the contents of epoxide butane structural unit A and epoxide butane structural unit B are obtained by calculation based on the amount of raw materials fed.

[0030] The aforementioned preferred polyols can exhibit low viscosity and narrow molecular weight distribution under conditions of high carbon dioxide fixation, as well as good water resistance and weather resistance.

[0031] Polyepoxybutane carbonate polyols possessing the aforementioned characteristics can achieve the objectives of this invention. There are no special requirements for their preparation methods. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the preparation method of the polyepoxybutane carbonate polyol includes: copolymerizing epoxybutane and carbon dioxide in the presence of a catalyst and an initiator.

[0032] In this invention, there are no special requirements for the copolymerization apparatus, etc. Any apparatus that can achieve the copolymerization requirements of this invention can be used in this invention. For example, the copolymerization can be carried out in a pressure vessel equipped with a pressure and temperature measuring instrument, a stirring device and a raw material inlet.

[0033] According to a preferred embodiment of the present invention, the epoxide is 1,2-epoxide and / or 2,3-epoxide, more preferably, the epoxide is a mixture of 1,2-epoxide and 2,3-epoxide, with a weight ratio of 0.1-10:1, preferably 0.5-2:1. The polyol synthesized using the aforementioned preferred method exhibits low viscosity and narrow molecular weight distribution under conditions of high carbon dioxide fixation, and possesses good water resistance and weather resistance.

[0034] In this invention, there are no special requirements for the type of catalyst. All commonly used catalysts in the prior art can be used in this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the catalyst is a polymetallic cyanide catalyst, preferably one or more of zinc hexacyanocobaltate complex, zinc hexacyanoferrate complex, and zinc tetracyanonitrile complex.

[0035] For example, the polymetallic cyanide catalyst has the following general formula:

[0036] M 1 a [M 2 d (CN) f ].M 1 b [M 3 e (CN) g ].M 1 c X h .Y i .Z j .kH2O, Equation (1);

[0037] In the formula:

[0038] M 1 M 3 Independently selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W, Cu, or Cr; among which, M 1 The preferred materials are Zn, Ni, or Co; M 3 The preferred form is Zn or Fe;

[0039] M 2Selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V, preferably Fe or Co;

[0040] X is selected from halogen elements, OH - NO3 - CO3 2- SO4 2- or ClO3 2- ;

[0041] Y is selected from C4-C having a tertiary alcohol structure. 10 Organic alcohols, preferably tert-butanol or tert-amyl alcohol;

[0042] Z is selected from aliphatic esters, aromatic monoesters or aromatic diesters, preferably aromatic diesters, and more preferably phthalates;

[0043] a, b, and c represent M 1 The number of ions; d and e represent M respectively. 2 M 3 Number of ions; f and g represent the number of CN ions; h, i, j, and k represent the number of X, Y, Z, and H2O ions, respectively. See CN 111087597 B for details.

[0044] In this invention, the polymetallic cyanide catalyst can achieve the purpose of this invention by satisfying the foregoing requirements, and there are no special requirements for its preparation method. For example, the preparation method of the polymetallic cyanide catalyst includes:

[0045] (1) Forming a metal cyanide complex by combining one or more metal cyanides with one or more metal salts under the action of an organic ligand;

[0046] (2) The catalyst was washed multiple times with the two organic ligands, centrifuged, and dried to obtain a solid powder. See CN 111087597 B for details.

[0047] The catalyst polymetallic cyanide used in the embodiments of this invention is a commercially available product from Sinopec (Shanghai) Petrochemical Research Institute, with the brand name SPEO-1.

[0048] In this invention, the range of types of initiators is relatively wide. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the initiator is an active hydrogen compound containing the structural formula -OH. Preferably, the initiator is one or more of the following: monohydric alcohols having 1-20 carbon atoms, polyhydroxy alcohols having 2-20 carbon atoms and 2-8 hydroxyl groups, and polyether polyols having 2-8 terminal groups with 1-8 hydroxyl groups on the terminal groups and a number average molecular weight of 200-30000.

[0049] According to a preferred embodiment of the present invention, the initiator is a monohydric alcohol having 1-20 carbon atoms, such as one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, and isoamyl alcohol; a polyhydroxy alcohol having 2-20 carbon atoms and 2-8 hydroxyl groups, such as one or more of ethylene glycol, propylene glycol, glycerol, diglycerol, butanediol, and pentaerythritol; or a sugar or its derivative, such as one or more of glucose, sorbitol, fructose, sucrose, and bisphenol A.

[0050] In this invention, the initiator is, for example, a carboxylic acid having 1-20 carbon atoms, such as one or more of formic acid, acetic acid, propionic acid, butyric acid, and lauric acid; or, for example, a polycarboxylic acid having 2-20 carbon atoms and 2-6 carboxyl groups, such as one or more of oxalic acid, malonic acid, succinic acid, maleic acid, and terephthalic acid.

[0051] All of the above-mentioned initiators are applicable to this invention. In the implementation of this invention, the advantages of this invention are illustrated by difunctional polyether polyol GEP-204 and trifunctional polyether polyol GEP-305, but this does not limit the scope of this invention.

[0052] In this invention, the weight ratio of catalyst to epoxide can be selected over a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the weight ratio of catalyst to epoxide is 3 × 10⁻⁶. -5 -2×10 -3 : 1, for example, 5×10 -5 : 1, 3.5 × 10 -4 1,8×10 -4 : 1, 1.5 × 10 -3 :1.

[0053] In this invention, the weight ratio of the initiator to epoxide can be selected from a wide range. The following is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the weight ratio of the initiator to epoxide is 0.01-2:1, for example, 0.05:1, 0.1:1, 0.2:1, 0.3:1.

[0054] In this invention, there are no special requirements for the copolymerization reaction temperature. Commonly used copolymerization reaction temperatures are applicable to this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the copolymerization reaction temperature is 60-170℃, preferably 100-120℃.

[0055] In this invention, the carbon dioxide pressure in the copolymerization reaction can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the carbon dioxide pressure in the copolymerization reaction is 0.2-10 MPa, preferably 1-5 MPa.

[0056] In this invention, the copolymerization reaction time has a wide range of options. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the copolymerization reaction time is 0.1-24h, preferably 0.5-16h.

[0057] The present invention provides a polyepoxybutane carbonate polyol prepared according to the method of the present invention, wherein the polyol has low viscosity and narrow molecular weight distribution under high carbon dioxide fixation conditions, and has good water resistance and weather resistance.

[0058] According to a preferred embodiment of the present invention, preferably, the polyol has a viscosity of 200-5000 mPa·s at 25°C.

[0059] According to a preferred embodiment of the present invention, preferably, the carbon dioxide fixation amount of the polyol is 10-30%.

[0060] According to a preferred embodiment of the present invention, preferably, the polyol has a molecular weight distribution of 1.0-1.3.

[0061] According to a preferred embodiment of the present invention, the polyol has a viscosity of 400-2000 mPa·s at 25°C, preferably 800-1000 mPa·s; and a carbon dioxide fixation content of 20-30%, preferably 20-25%.

[0062] According to a preferred embodiment of the present invention, the number average molecular weight is preferably 200-6000, more preferably 400-4000, and even more preferably 3400-3800.

[0063] According to a preferred embodiment of the present invention, preferably, the molecular weight distribution is 1.0-1.25.

[0064] According to a preferred embodiment of the present invention, the polyol includes epoxide butane structural unit A and / or epoxide butane structural unit B;

[0065] The structural formula of epoxide structural unit A is:

[0066] The structural formula of epoxide structural unit B is:

[0067] According to a preferred embodiment of the present invention, the polyol preferably includes epoxide butane structural unit A and epoxide butane structural unit B, and the weight ratio of the two is 0.1-10:1, preferably 0.5-2:1.

[0068] The aforementioned preferred polyepoxybutane carbonate polyol has low viscosity and narrow molecular weight distribution, and exhibits good water resistance and weather resistance.

[0069] This invention provides the application of the polyepoxybutane carbonate polyol described herein in the preparation of adhesives, coatings, sealants, and elastomers. The polyepoxybutane carbonate polyol of this invention exhibits low viscosity and a narrow molecular weight distribution under high carbon dioxide fixation conditions, and possesses good water resistance and weather resistance, making it particularly suitable for the preparation of adhesives, coatings, sealants, and elastomers.

[0070] This invention provides an adhesive prepared by reacting raw materials including the polyepoxybutane carbonate polyol and curing agent described in this invention; preferably, the adhesive has a tensile strength of 5-7 MPa, more preferably 5.5-6 MPa; an elongation at break of 200-300%; and a bond strength of 3-5 MPa, more preferably 3.5-4 MPa.

[0071] In this invention, there are no special requirements for the type of curing agent. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the curing agent is one or more of isocyanates, amines, and acid anhydrides. It is preferably an isocyanate containing an average of at least 2.0 isocyanate groups per molecule, and more preferably an isocyanate with an isocyanate functionality of about 2.0-3.0 or 2.0-2.5 groups per molecule, such as polymeric MDI, for example, isocyanate PM200.

[0072] In this invention, there are no special requirements for the amount of polyepoxybutane carbonate polyol and curing agent. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the weight ratio of polyepoxybutane carbonate polyol and curing agent is 1:0.01-0.2, preferably 1:0.05-0.15.

[0073] In this invention, there are no special requirements for the curing reaction temperature. Commonly used curing reaction temperatures are applicable to this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the curing reaction temperature is 60-150℃, for example, 70℃, 90℃, 110℃, or 130℃.

[0074] In this invention, the curing reaction time can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the curing reaction time is 2-48h, for example, 8h, 12h, 16h, 20h, 24h, 28h, 32h, 36h.

[0075] The present invention provides a method for preparing an adhesive, the method comprising: mixing polyepoxybutane carbonate polyol with a curing agent, a second polyol, a chain extender and a catalyst, and then curing.

[0076] In this invention, there are no special requirements for the type of curing agent. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the curing agent is one or more of isocyanates, amines, and acid anhydrides. It is preferably an isocyanate containing an average of at least 2.0 isocyanate groups per molecule, and more preferably an isocyanate with an isocyanate functionality of about 2.0-3.0 or 2.0-2.5 groups per molecule, such as polymeric MDI, for example, isocyanate PM200.

[0077] In this invention, the range of second polyols is relatively wide. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the second polyol is a fatty alcohol and / or a vegetable oil containing at least 2 hydroxyl groups per molecule, preferably castor oil.

[0078] In this invention, there are no special requirements for the type of chain extender. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the chain extender is a small molecule compound containing at least two hydroxyl groups and / or two amino groups per molecule, preferably one or more of ethylene glycol, 1,4-butanediol, 1,3-propanediol, diethylene glycol, and triethylene glycol.

[0079] In this invention, the range of catalysts that can be selected is relatively wide, and commonly used types can achieve the purpose of this invention. Those skilled in the art can select and use them as needed. For example, tin catalysts can be selected from one or more of stannous octoate, dibutyltin dilaurate, and tin acetate.

[0080] In this invention, there are no special requirements for the amounts of the polyepoxybutane carbonate polyol, curing agent, second polyol, chain extender, and catalyst. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the weight ratio of the polyepoxybutane carbonate polyol, curing agent, second polyol, chain extender, and catalyst is 1:0.01-0.2:0.2-0.5:0.04-0.07:0.0004-0.0007, preferably 1:0.05-0.15:0.3-0.5:0.05-0.07:0.0005-0.0007.

[0081] In this invention, there are no special requirements for the curing reaction temperature. Commonly used curing reaction temperatures are applicable to this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the curing reaction temperature is 60-150℃, for example, 70℃, 90℃, 110℃, or 130℃.

[0082] In this invention, the curing reaction time can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the curing reaction time is 2-48 hours.

[0083] The present invention provides an adhesive prepared by the preparation method described herein. Preferably, the adhesive has a tensile strength of 5-7 MPa, more preferably 5.5-6 MPa; an elongation at break of 200-300%; and a bond strength of 3-5 MPa, more preferably 3.5-4 MPa.

[0084] The adhesive described in this invention is particularly suitable for applications in the fields of construction, automotive, and aerospace.

[0085] In the embodiments, unless otherwise specified, the parts used refer to parts by weight.

[0086] In this invention, the 1H NMR spectrum of the copolymerization product was characterized using JNM-ECZ 500MHz NMR.

[0087] The number-average molecular weight and molecular weight distribution of the polymers were determined by GPC. The instrument was a Waters e2695. The column temperature was 35℃, the mobile phase was tetrahydrofuran (THF), and the flow rate was 1 ml / min. Polystyrene was used as a standard.

[0088] Viscosity tests were performed on a BrookField DV2T viscometer.

[0089] The carbon dioxide fixation (in mole fraction) was calculated using the 1H NMR spectrum of poly(epoxybutane carbonate) polyol. The specific calculation formula is as follows:

[0090]

[0091] Among them, A 4.73 A represents the peak area at 4.73 in the product's 1H NMR spectrum. 4.64 A represents the peak area at 4.64 in the product's 1H NMR spectrum. 4.5 A represents the peak area at 4.5 in the product's 1H NMR spectrum. 0.89 This represents the peak area at 0.89 in the product's 1H NMR spectrum.

[0092] Preparation Example 1

[0093] 40g of difunctional polyether polyol GEP-204 (molecular weight 400) and 0.06g of SPEO-1 polymetallic cyanide complex were added to a 0.5L pressure vessel equipped with pressure and temperature gauges, a stirring device, and a raw material inlet. After carbon dioxide replacement, the temperature was raised to 110℃, and the carbon dioxide pressure was increased to 3 MPa. 160g of 1,2-epoxybutane was continuously added over 6 hours. After feeding, the mixture was matured for 2 hours, the carbon dioxide was vented, and 225g of product was discharged. This product contained 184g of polymer and 41g of butenyl carbonate (18%). The polymer's number-average molecular weight was 3344, its molecular weight distribution was 1.16, and its viscosity at 25℃ was 939 mPa·s. The product's 1H NMR spectrum (see [link to product details]) was analyzed. Figure 1 The carbon dioxide fixation rate is calculated to be 20%.

[0094] Preparation Example 2

[0095] 50g of trifunctional polyether polyol GEP-305 (molecular weight 500) and 0.06g of SPEO-1 polymetallic cyanide complex were added to a 0.5L pressure vessel equipped with pressure and temperature gauges, a stirring device, and a raw material inlet. After carbon dioxide replacement, the temperature was raised to 110℃, and the carbon dioxide pressure was increased to 3 MPa. 150g of 1,2-epoxybutane was continuously added over 6 hours. After feeding, the mixture was matured for 2 hours, the carbon dioxide was vented, and 220g of product was discharged. This product contained 185g of polymer and 35g of butenyl carbonate (16%). The polymer had a number-average molecular weight of 3100, a molecular weight distribution of 1.18, a carbon dioxide fixation of 21%, and a viscosity of 1030 mPa·s.

[0096] Preparation Example 3

[0097] 40g of difunctional polyether polyol GEP-204 (molecular weight 400) and 0.06g of SPEO-1 polymetallic cyanide complex were added to a 0.5L pressure vessel equipped with pressure and temperature gauges, a stirring device, and a raw material inlet. After carbon dioxide replacement, the temperature was raised to 110℃, and the carbon dioxide pressure was increased to 1.5 MPa. 160g of 1,2-epoxybutane was continuously added over 6 hours. After feeding, the mixture was matured for 2 hours, the carbon dioxide was vented, and 215g of product was discharged. This product contained 185g of polymer and 30g of butenyl carbonate (14%). The polymer's number-average molecular weight was 3020, its molecular weight distribution was 1.29, and its viscosity was 436 mPa·s. The product's 1H NMR spectrum (see [link to product details]) was analyzed. Figure 2 The carbon dioxide fixation rate is calculated to be 10%.

[0098] Preparation Example 4

[0099] 40g of difunctional polyether polyol GEP-204 (molecular weight 400) and 0.06g of SPEO-1 polymetallic cyanide complex were added to a 0.5L pressure vessel equipped with pressure and temperature gauges, a stirring device, and a raw material inlet. After carbon dioxide replacement, the temperature was raised to 110℃, and the carbon dioxide pressure was increased to 3 MPa. Over 6 hours, a mixture of 100g of 1,2-epoxybutane and 60g of 2,3-epoxybutane was continuously added. After feeding, the mixture was matured for 2 hours, the carbon dioxide was vented, and 228g of product was discharged. This included 208g of polymer and 20g of butenyl carbonate (8.8%). The polymer's number-average molecular weight was 3444, its molecular weight distribution was 1.20, and its viscosity was 875 mPa·s. The carbon dioxide fixation content, calculated from the product's 1H NMR spectrum, was 22%.

[0100] Preparation Example 5

[0101] 40g of difunctional polyether polyol GEP-204 (molecular weight 400) and 0.06g of SPEO-1 polymetallic cyanide complex were added to a 0.5L pressure vessel equipped with pressure and temperature gauges, a stirring device, and a raw material inlet. After carbon dioxide replacement, the temperature was raised to 110℃, and the carbon dioxide pressure was increased to 3 MPa. Over 6 hours, a mixture of 80g of 1,2-epoxybutane and 80g of 2,3-epoxybutane was continuously added. After feeding, the mixture was matured for 2 hours, the carbon dioxide was vented, and 230g of product was discharged. This product contained 210g of polymer and 20g of butenyl carbonate (8.7%). The polymer had a number-average molecular weight of 3750, a molecular weight distribution of 1.21, and a viscosity of 1000 mPa·s. Based on the product's 1H NMR spectrum, the carbon dioxide fixation content was calculated to be 24%.

[0102] Preparation Example 6

[0103] 40g of difunctional polyether polyol GEP-204 (molecular weight 400) and 0.06g of SPEO-1 polymetallic cyanide complex were added to a 0.5L pressure vessel equipped with pressure and temperature gauges, a stirring device, and a raw material inlet. After carbon dioxide replacement, the temperature was raised to 110℃, and the carbon dioxide pressure was increased to 3 MPa. Over 6 hours, a mixture of 60g of 1,2-epoxybutane and 100g of 2,3-epoxybutane was continuously added. After feeding, the mixture was matured for 2 hours, the carbon dioxide was vented, and 229g of product was discharged. This product contained 210g of polymer and 19g of butenyl carbonate (8.3%). The polymer's number-average molecular weight was 3724, its molecular weight distribution was 1.21, and its viscosity was 975 mPa·s. Based on the product's 1H NMR spectrum, the carbon dioxide fixation content was calculated to be 23%.

[0104] Preparation Example 7

[0105] 40g of a difunctional polyether polyol GEP-204 with a molecular weight of 400 and 0.06g of a SPEO-1 polymetallic cyanide complex were added to a 0.5L pressure vessel equipped with pressure and temperature gauges, a stirring device, and a raw material inlet. After carbon dioxide replacement, the temperature was raised to 110℃, and the carbon dioxide pressure was increased to 3 MPa. Over 6 hours, a mixture of 160g of 2,3-epoxybutane was continuously added. After feeding, the mixture was matured for 2 hours, the carbon dioxide was vented, and 225g of product was discharged. This product contained 205g of polymer and 20g of butenyl carbonate (8.9%). The polymer had a number-average molecular weight of 3500, a molecular weight distribution of 1.22, and a viscosity of 900 mPa·s. Based on the product's 1H NMR spectrum, the carbon dioxide fixation content was calculated to be 20%.

[0106] Adhesive Preparation Examples 1-7

[0107] Weigh out 70 parts of polyepoxybutane carbonate polyol prepared in each preparation example, along with 30 parts of castor oil, 4.5 parts of 1,4-butanediol, and 0.04 parts of tin catalyst stannous octoate, and stir until homogeneous. Then, according to an isocyanate index of 1.02, add polymeric MDI (isocyanate PM200) to obtain the adhesive. The curing temperature is 80℃, and the curing time is 6 hours. The performance test results are listed in Table 1.

[0108] Comparative Example 1 for Adhesive Preparation

[0109] 70 parts of a bifunctional polyoxypropylene carbonate polyol with a molecular weight of 3000, 30 parts of castor oil, 4.5 parts of 1,4-butanediol, and approximately 0.04 parts of tin catalyst stannous octoate were weighed and stirred until homogeneous. Then, polymerized MDI was added according to an isocyanate index of 1.02 to obtain the adhesive. The curing temperature was 80℃, and the curing time was 6 hours. The performance test results are listed in Table 1.

[0110] Comparative Example 2 of Adhesive Preparation

[0111] 70 parts of poly(epoxybutanediol) with a molecular weight of 3000, 30 parts of castor oil, 4.5 parts of 1,4-butanediol, and approximately 0.04 parts of tin catalyst stannous octoate were weighed and stirred until homogeneous. Then, polymerized MDI was added according to an isocyanate index of 1.02 to obtain the adhesive. The curing temperature was 80℃, and the curing time was 72 hours. The performance test results are listed in Table 1.

[0112] Tensile strength and elongation at break were tested according to ASTM D638. Bond strength was tested according to ASTM D1002.

[0113] Water absorption test method: Immerse the cured polymer in water for 72 hours at a temperature of about 25°C, and then measure the weight change.

[0114] Table 1

[0115]

[0116]

[0117] By comparing the examples and comparative examples, the adhesive of the present invention has excellent water resistance and better mechanical properties.

[0118] The preferred embodiments of the present invention have been described above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various specific technical features in any suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A polybutylene oxide carbonate polyol characterized in that, The polyol has a viscosity of 200-5000 mPa s at 25℃, a carbon dioxide fixation amount of 10-30%, and a molecular weight distribution of 1.0-1.

3.

2. The polyol of claim 1, wherein, The polyol has a viscosity of 200-5000 mPa s at 25℃, a carbon dioxide fixation amount of 10-30%, and a molecular weight distribution of 1.0-1.

3. The polyol has a viscosity of 400-2000 mPa s at 25℃, preferably 800-1000 mPa s; and / or The polyol has a carbon dioxide fixation amount of 20-30%, preferably 20-25%; and / or The polyol has a number average molecular weight of 200-6000, preferably 400-4000, more preferably 3400-3800; and / or The polyol has a molecular weight distribution of 1.0-1.

25. The polyol includes the butylene oxide structural unit A and / or the butylene oxide structural unit B; 3. The polyol of claim 1 or 2, wherein, Preferably, the polyol includes the butylene oxide structural unit A and the butylene oxide structural unit B, and the weight ratio of the two is 0.1-10:1, preferably 0.5-2:

1. The structural formula of the butylene oxide structural unit A is: The structural formula of the butylene oxide structural unit B is: The method includes: copolymerizing butylene oxide and carbon dioxide in the presence of a catalyst and a starter.

4. A process for the preparation of a polytetramethylene oxide carbonate polyol characterized by, The butylene oxide is 1,2-butylene oxide and / or 2,3-butylene oxide; more preferably, the butylene oxide is a mixture of 1,2-butylene oxide and 2,3-butylene oxide, and the weight ratio of the two is 0.1-10:1, preferably 0.5-2:

1.

5. The production method according to claim 4, wherein 6. The preparation method according to claim 4 or 5, wherein, The catalyst is one or more of zinc hexacyanocobaltate, zinc hexacyanoferrate, and zinc tetracyanonickelate; and / or The starter is an active hydrogen compound containing the structural formula -OH; Preferably, The starter is one or more of a monohydric alcohol having 1-20 carbon atoms, a polyhydric alcohol having 2-20 carbon atoms and 2-8 hydroxyl groups, a polyether polyol having 2-8 end groups and 1-8 hydroxyl groups on the end groups and a number average molecular weight of 200-30000, a monobasic carboxylic acid having 1-20 carbon atoms, and a polybasic carboxylic acid having 2-20 carbon atoms and 2-6 carboxyl groups. The copolymerization reaction conditions include:

7. The method of making according to any one of claims 4-6, wherein, The weight ratio of the amount of the starter to the amount of the butylene oxide is 0.01-2:1; and / or The catalyst to butylene oxide is used in a weight ratio of 3 x 10 -5 -2 x 10 -3 : 1; and / or The temperature is 60-170℃, preferably 100-120℃; and / or The carbon dioxide pressure is 0.2-10 MPa, preferably 1-5 MPa; and / or The time is 0.1-24 h, preferably 0.5-16 h.

8. The polybutylene oxide carbonate polyol obtained by the preparation method of any one of claims 4-7, Preferably, the polyol has a viscosity of 200-5000 mPa s at 25℃, a carbon dioxide fixation amount of 10-30%, and a molecular weight distribution of 1.0-1.3; More preferably, The polyol has a viscosity of 400-2000 mPa s at 25℃, preferably 800-1000 mPa s; The polyol has a carbon dioxide fixation amount of 20-30%, preferably 20-25%; and / or The polyol has a number average molecular weight of 200-6000, preferably 400-4000, more preferably 3400-3800; and / or The polyol has a molecular weight distribution of 1.0-1.25; and / or ​ ​ ​ More preferably, the polyol comprises the butylene oxide structural unit A and / or the butylene oxide structural unit B; The structural formula of the butylene oxide structural unit A is: The structural formula of the butylene oxide structural unit B is: Further preferably, the polyol comprises the butylene oxide structural unit A and the butylene oxide structural unit B, and the weight ratio of the two is 0.1-10:1, preferably 0.5-2:

1.

9. Use of the polybutylene oxide carbonate polyol according to any one of claims 1-3, 8 in the preparation of adhesives, coatings, sealants, elastomers.

10. An adhesive characterized by, The adhesives are prepared by reacting the raw materials of the polybutylene oxide carbonate polyol according to any one of claims 1-3, 8 and a curing agent; preferably, the tensile strength of the adhesives is 5-7 MPa, preferably 5.5-6 MPa; the elongation at break is 200-300%; the bonding strength is 3-5 MPa, preferably 3.5-4 MPa.

11. The adhesive according to claim 10, wherein, the curing agent is one or more of isocyanate, amine, acid anhydride compounds, preferably isocyanate with an average of at least 2.0 isocyanate groups per molecule, more preferably isocyanate with an isocyanate functionality of 2.0-3.0 or 2.0-2.5 per molecule, more preferably polymeric MDI; and / or the weight ratio of the polybutylene oxide carbonate polyol and the curing agent is 1:0.01-0.2, preferably 1:0.05-0.15; and / or the reaction conditions include a temperature of 60-150℃ and / or a time of 2-48h.

12. A method of producing an adhesive, characterized by, The method comprises mixing the polybutylene oxide carbonate polyol, a curing agent, a second polyol, a chain extender and a catalyst, and then curing; the polybutylene oxide carbonate polyol is the polybutylene oxide carbonate polyol according to any one of claims 1-3, 8; Preferably, the curing agent is one or more of isocyanate, amine, acid anhydride compounds, preferably isocyanate with an average of at least 2.0 isocyanate groups per molecule, more preferably isocyanate with an isocyanate functionality of 2.0-3.0 or 2.0-2.5 per molecule, more preferably polymeric MDI; and / or the second polyol is a fatty alcohol with an average of at least 2 hydroxyl groups per molecule and / or a vegetable oil with at least 2 hydroxyl groups, preferably castor oil; and / or the chain extender is a small molecule compound with at least 2 hydroxyl groups and / or 2 amine groups per molecule, preferably one or more of ethylene glycol, 1,4-butanediol, 1,3-propanediol, diethylene glycol and triethylene glycol; and / or the weight ratio of the polybutylene oxide carbonate polyol, the curing agent, the second polyol, the chain extender and the catalyst is 1:0.01-0.2:0.2-0.5:0.04-0.07:0.0004-0.0007, preferably 1:0.05-0.15:0.3-0.5:0.05-0.07:0.0005-0.0007; and / or the curing reaction conditions include a temperature of 60-150℃ and / or a time of 2-48h.

13. The adhesive prepared by the method of claim 12, preferably, the tensile strength of the adhesive is 5-7 MPa, preferably 5.5-6 MPa; the elongation at break is 200-300%; the bonding strength is 3-5 MPa, preferably 3.5-4 MPa.

14. Use of the adhesive of claim 10, 11 or 13 in the fields of construction, automobile, aerospace.

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