A C9 hydrocarbon resin-based polyisocyanate resin and its preparation method

Abstract

The present invention relates to the technical field of polyurethane preparation, and discloses a C9 hydrocarbon resin-based polyisocyanate and a preparation method thereof. Through the grafting reaction of C9-HCR with polyisocyanate, C9 hydrocarbon resin-based polyisocyanate C9-HCI resin is prepared; in the process method for preparing phenol-modified liquid hydrocarbon resin C9-HCR in the present invention, through the effective control of the hydroxyl content, viscosity and moisture in the C9-HCR product, it provides beneficial technical support for realizing the isocyanation of C9-HCR hydrocarbon resin; the grafting reaction of C9-HCR with polyisocyanate is carried out under the catalysis of dibutyltin dilaurate, and the polyisocyanate monomer reacting with C9-HCR resin can be selected from one or more of TDI and its isomers, or MDI and its isomers; the proportion of the dibutyltin dilaurate catalyst is 0.05% to 0.5% of the weight of the reactants, the reaction temperature is controlled at 60 to 80 degrees, and the reaction is carried out for 2 to 6 hours, and finally C9-HCI resin is obtained, realizing the isocyanation of C9-HCR hydrocarbon resin.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane preparation, and specifically to a C9 hydrocarbon resin-based polyisocyanate resin and a preparation method thereof. Background Art

[0002] The main components of C9 fractions are by-products in the processes of ethylene production by cracking and catalytic reforming in petroleum refining. Generally, it contains about 50% of active monomers. These active components can also be divided into two categories. One category is aromatic olefins with monofunctionality such as styrene, methylstyrene, and indene. The other category is alicyclic olefins with difunctionality such as dicyclopentadiene and methyl dicyclopentadiene (DCPD). The resinous substances formed by the chemical reaction polymerization of these active monomers are collectively called C9 hydrocarbon resins (C9 Hydrocarbon Resins, abbreviated as C9-HCR). The outstanding advantage of C9-HCR petroleum resins is their low price, and they have good hydrophobicity, acid and alkali resistance, salt spray resistance and other properties. They have been promoted and applied in many chemical product fields, such as coatings, adhesives, rubbers, inks, and building materials.

[0003] Various materials for polyurethane preparation, such as coils, foam materials, coatings, adhesives, and mastics, have been widely used in the construction field. Especially for the above materials applied in the waterproof field, C9-HCR petroleum resins are often used as modified resins for polyurethanes. On the one hand, it can reduce the manufacturing cost of polyurethane materials. At the same time, it can also improve the surface drying speed of polyurethane waterproof building materials, as well as the water resistance, corrosion resistance, heat resistance and other properties after curing. However, when C9-HCR resin is used as a non-reactive filling resin or a blend modified resin for polyurethane building materials, since it cannot form a cross-linked network with the main resin part, when the amount of petroleum resin in polyurethane is too much, the excess petroleum resin will be free in the system, which will reduce the intermolecular interaction force, and then affect the mechanical properties of the cured polyurethane materials. Therefore, only a small amount of non-reactive petroleum resin can be accommodated in the polyurethane solidified body, which cannot effectively reduce the manufacturing cost of polyurethane, and its contribution to improving the performance of polyurethane materials is limited. Therefore, it is very necessary to develop a reactive C9 hydrocarbon resin capped with an isocyanate group (-NCO). Therefore, a C9 hydrocarbon resin-based polyisocyanate and a preparation method thereof are proposed to solve the above problems. Summary of the Invention

[0004] (I) Technical Problems to be Solved

[0005] In view of the deficiencies of the prior art, the present invention provides a C9 hydrocarbon resin-based polyisocyanate resin (C9-HCI) and a preparation method thereof; the phenol-modified liquid hydrocarbon resin C9-HCR prepared by the present invention can realize the isocyanation of the C9-HCR resin by controlling parameters such as the hydroxyl value, viscosity and water content in the C9-HCR, and finally obtain the C9 hydrocarbon resin-based polyisocyanate C9-HCI resin; the C9-HCI resin prepared by the present invention is applied to polyurethane materials. On the one hand, it can reduce the manufacturing cost of polyurethane materials, and on the other hand, it can effectively improve the mechanical properties, water resistance and chemical corrosion resistance of polyurethane materials; the C9-HCI resin prepared by the present invention is particularly suitable for preparing waterproof polyurethane materials.

[0006] (II) Technical Solution

[0007] To achieve the reduction of the manufacturing cost of the above-mentioned polyurethane materials and at the same time effectively improve their mechanical properties, water resistance and excellent chemical corrosion resistance, the present invention provides the following technical solutions: a C9 hydrocarbon resin-based polyisocyanate resin and a preparation method thereof. One of the purposes is to provide a phenol-modified liquid hydrocarbon resin C9-HCR that can be isocyanated; the second is to provide a preparation method of a C9 hydrocarbon resin-based polyisocyanate (C9-HCI) resin; the third is to relate to using the C9 hydrocarbon resin-based polyisocyanate (C9-HCI) as the matrix of the polyurethane resin to prepare a polyurethane adhesive that can be cured at room temperature.

[0008] This technical solution includes the following steps:

[0009] S1, prepare the phenol-modified liquid hydrocarbon resin C9-HCR,

[0010] (1) Under an inert gas atmosphere, add the phenolic monomer containing hydroxyl groups and the C9 aromatic olefin monomer together to a reactor beaker containing xylene solvent, control the weight ratio of the reaction monomers to the solvent to be 1:1, and start stirring to mix the above reaction monomers and solvent evenly. The xylene solvent is the reaction medium;

[0011] The phenolic monomer containing hydroxyl groups can be selected from any one or more of the following structures:

[0012]

[0013] The C9 aromatic olefin monomer can be selected from any one or more of the following structures:

[0014] R1 can be CH3 or H respectively.

[0015] (2) After the monomer to be reacted is mixed evenly with the solvent, the temperature of the reactor is controlled within the range of 10 - 60 °C. While stirring, the cationic initiator BF3·Et2O is slowly added dropwise. The dosage of the BF3·Et2O initiator accounts for 0.1 - 3% of the total amount of monomers used in the synthesis of C9 - HCR resin;

[0016] (3) After the initiator is added dropwise, the reaction is carried out for 2 - 6 hours under the constant temperature condition of 10 - 60 °C;

[0017] (4) After the above cationic polymerization reaction is completed, an appropriate amount of 10% Na2CO3 alkaline solution is taken and added into the reactor flask, and the temperature of the reactor is raised to 50 - 80 °C for alkali washing for 0.5 - 1 hour;

[0018] (5) The reactant after alkali washing is washed with deionized water multiple times under the condition of 70 - 80 °C until the pH value of the reactant reaches 7 (neutral) and then the washing is stopped; Then, the neutral reaction product is subjected to oil - water separation to obtain the crude phenolic - modified liquid C9 - HCR resin;

[0019] (6) The crude phenolic - modified liquid C9 - HCR resin is poured into a distillation flask, and vacuum distillation is carried out to remove inert solvents, water, and unreacted small molecules, etc. The temperature of the vacuum distillation is controlled at 90 - 110 °C, and the vacuum degree is controlled at 0.05 - 0.1 MPa, and finally the refined phenolic - modified liquid C9 - HCR resin is obtained;

[0020] (7) The finally refined phenolic - modified liquid hydrocarbon resin C9 - HCR has a hydroxyl value within the range of 60 - 300 mgKOH / g, a viscosity within the range of 500 - 3000 mPa·s, and the water content is controlled below 0.01%;

[0021] S2. Based on the phenolic - modified liquid hydrocarbon resin (C9 - HCR) prepared in step S1, C9 - HCI resin is prepared through a grafting reaction with polyisocyanate; In the grafting reaction of C9 - HCR resin and polyisocyanate, the molar ratio of the hydroxyl group in C9 - HCR resin to the isocyanate group in polyisocyanate is 1:2.2, that is, mole(-OH):mole(-NCO) = 1:2.2, so as to achieve complete substitution of phenolic hydroxyl groups by isocyanate;

[0022] S3. In the grafting reaction of C9 - HCR resin and polyisocyanate, the polyisocyanate monomer reacting with C9 - HCR resin can be selected from one or more of TDI and its isomers, or MDI and its isomers;

[0023] S4. The grafting reaction of C9-HCR resin and polyisocyanate is carried out under the catalysis of dibutyltin dilaurate, and the proportion of the dibutyltin dilaurate catalyst is 0.05% - 0.5% of the weight of the reactants; the reaction temperature is controlled at 60 - 80 °C, and the reaction is carried out for 2 - 6 hours to finally obtain C9-HCI resin;

[0024] S5. For the C9-HCI resin finally prepared by the grafting reaction of C9-HCR resin and polyisocyanate, the mass fraction of isocyanate group (-NCO) therein is controlled at 2 - 10%, and the viscosity can be controlled at 800 - 5000 mPa·s.

[0025] Preferably, the C9-HCI resin prepared in the steps S2 - S5 is used as the matrix, and combined with other raw materials commonly used for preparing polyurethane adhesives, a new type of polyurethane adhesive is prepared.

[0026] Preferably, the C9-HCI resin-based polyurethane adhesive includes C9-HCI resin, PMDI resin, flame retardant, and silicate. Among them, PMDI is preferably PM-200 produced by Wanhua Chemical, the flame retardant is a phosphorus-based flame retardant, preferably commercially available industrial grade trichloropropyl phosphate (TCPP), and the aqueous silicate solution is preferably commercially available water glass with a Baume degree of 50% and a modulus of 2.2 - 2.8.

[0027] Preferably, for the C9-HCI resin-based polyurethane adhesive that can be cured at room temperature, its curing speed is characterized by measuring the gel time; the mechanical strength after curing is characterized by testing the flexural strength and flexural modulus of the casting body. The flexural strength after curing > 40 MPa, and the flexural modulus > 4000 MPa. This C9-HCI resin-based polyurethane adhesive has excellent mechanical strength after curing at room temperature and can be widely used in infrastructure fields such as municipal waterproof projects.

[0028] (III) Beneficial effects

[0029] Compared with the prior art, the present invention provides a C9 hydrocarbon resin-based polyisocyanate and its preparation method, which have the following beneficial effects:

[0030] 1. A phenol-modified liquid hydrocarbon resin (C9-HCR) and its preparation method can effectively control parameters such as the hydroxyl content, viscosity, and moisture in the C9-HCR resin, providing beneficial technical support for the preparation of C9-HCI resin.

[0031] 2. On the basis of the phenol-modified liquid hydrocarbon resin C9-HCR, by selecting a suitable catalyst system and polyisocyanate reactants, through the grafting reaction of C9-HCR resin and polyisocyanate, the isocyanation modification of C9-HCR resin is realized, and the C9 hydrocarbon resin-based polyisocyanate C9-HCI resin is obtained.

[0032] 3. When applying C9 hydrocarbon resin-based polyisocyanate (C9-HCI) resin to polyurethane adhesives, the cured mechanical strength is relatively good. At the same time, the water resistance, chemical medium corrosion resistance, and heat resistance of such polyurethane adhesives are improved, expanding the application range of C9 hydrocarbon resin. Specific embodiments

[0033] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0034] Embodiment 1:

[0035] S1. Place the raw materials of the C9-HCR reactant in Example 1, namely α-methylstyrene, indene, styrene, and phenol, into a four-necked flask containing xylene solvent at room temperature; start the stirrer and uniformly dissolve all the reaction materials in the xylene solvent.

[0036] S2. Control the temperature of the reactor at 30°C and start dropping the initiator slowly, controlling the dropping rate of the initiator, and complete the dropping of the initiator in the formula within 10 minutes.

[0037] S3. After the initiator is dropped, start the reaction under the constant temperature condition of 30°C and control the constant temperature time to be 2.5 hours.

[0038] S4. After the reaction is completed, take an appropriate amount of 10% Na2CO3 solution by mass fraction, add it to the flask and stir evenly, and raise the temperature to 70°C for 30 minutes of alkali washing.

[0039] S5. After the alkalinity is completed, add deionized water to the flask and heat it to 80°C for water washing, and then separate the water and oil; repeat the water washing and separation operations 4 times until the pH of the washing liquid is neutral, and pour the upper oil-phase organic liquid into the distillation flask.

[0040] S6. Pour the resin organic liquid after water washing into a weighed distillation flask, connect the round-bottom flask to the vacuum distillation device, and check the airtightness of each ground glass interface of the device; turn on the condensate water, vacuum pump, and heating jacket switches respectively, start distillation, control the vacuum degree to be 0.06 MPa, the distillation temperature to be 100°C, and when there is no distillate in the system after 1 hour of distillation, obtain the C9-HCR-1 resin product, and test the viscosity, hydroxyl value, and moisture content of the C9-HCR-1 resin, and calculate the yield of the C9-HCR-1 resin product.

[0041] S7. Take 100 g of C9-HCR-1 resin, add dibutyltin dilaurate, start stirring, heat up to 70 °C, and then start dropping MDI-50. Finish dropping within 30 minutes, keep reacting at 70 °C for 4 hours, and finally obtain C9-HCI-1 resin with a viscosity of 3500 mPa·s and an -NCO content of 3%.

[0042] Table 1 Recipe of Example 1

[0043]

[0044]

[0045] Example Two:

[0046] S1. Place the C9-HCR reactant raw materials α-methylstyrene, indene, styrene and o-methylphenol in Example Two at room temperature in a four-necked flask already containing xylene solvent; start the stirrer and disperse all the reaction materials evenly in the xylene solvent;

[0047] S2. Control the temperature of the reactor at 30 °C, and start dropping the initiator slowly, controlling the dropping rate of the initiator, and finish dropping the initiator in the formula within 10 minutes;

[0048] S3. After the initiator dropping is completed, start reacting under the constant temperature condition of 30 °C, and control the constant temperature time to be 2.5 hours;

[0049] S4. After the reaction is completed, take an appropriate amount of 10% Na2CO3 solution by mass fraction, add it to the flask and stir evenly, and heat up to 70 °C for 30 minutes of alkali washing;

[0050] S5. After the alkalinity is completed, add deionized water to the flask and heat it to 80 °C for water washing, and then separate the water and oil; repeat the water washing and separation work 4 times until the pH of the washing liquid is neutral, and pour the upper oil-phase organic liquid into the distillation flask;

[0051] S6. Pour the washed resin organic liquid into the weighed distillation flask, connect the round-bottom flask to the vacuum distillation device, and check the airtightness of each ground glass joint of the device; turn on the condensate water, vacuum pump and heating jacket switches respectively, start distillation, control the vacuum degree to be 0.06 MPa, the distillation temperature to be 100 °C, and when there is no distillate in the system after 1 hour of distillation, obtain the C9-HCR-2 resin product, and test the viscosity, hydroxyl value, moisture content of the C9-HCR-2 resin, and calculate the yield of the C9-HCR-2 resin product;

[0052] S7. Take 100 g of C9-HCR-2 resin, add dibutyltin dilaurate, start stirring, heat up to 70 °C, and then start dropping MDI-50. Finish dropping within 30 minutes, keep reacting at 70 °C for 4 hours, and finally obtain C9-HCI-2 resin with a viscosity of 3000 mPa·s and an -NCO content of 6.5%.

[0053] Table 2 Recipe of Example 2

[0054]

[0055] Example Three:

[0056] S1. Place the C9-HCR reactant raw materials α-methylstyrene, indene, styrene and resorcinol in Example Three at room temperature in a four-necked flask already containing xylene solvent; start the stirrer and disperse all the reaction materials evenly in the xylene solvent.

[0057] S2. Control the temperature of the reactor at 30 °C, and start dropping the initiator slowly, controlling the dropping rate of the initiator, and finish dropping the initiator in the formula within 10 minutes.

[0058] S3. After the initiator is dropped, start reacting under the constant temperature condition of 30 °C, and control the constant temperature time to be 2.5 hours.

[0059] S4. After the reaction is completed, take an appropriate amount of 10% Na2CO3 solution by mass fraction, add it to the flask and stir evenly, and heat up to 70 °C for 30 minutes of alkali washing.

[0060] S5. After the alkalinity is completed, add deionized water to the flask and heat it to 80 °C for water washing, and then separate the water and oil; repeat the water washing and separation work 4 times until the pH of the washing liquid is neutral, and pour the upper oil-phase organic liquid into the distillation flask.

[0061] S6. Pour the washed resin organic liquid into a weighed distillation flask, connect the round-bottom flask to the vacuum distillation device, and check the airtightness of each ground glass joint of the device; turn on the condensate water, vacuum pump and heating jacket switches respectively, start distillation, control the vacuum degree to be 0.06 MPa, the distillation temperature to be 100 °C, and when there is no distillate in the system after distillation for 1 hour, obtain the C9-HCR-3 resin product, and test the viscosity, hydroxyl value and moisture content of the C9-HCR-3 resin, and calculate the yield of the C9-HCR-3 resin product.

[0062] S7. Take 100 g of C9-HCR-3 resin, add dibutyltin dilaurate, start stirring, heat up to 70 °C, and then start dropping MDI-50 was added dropwise within 30 minutes and reacted at a temperature of 70 °C for 4 hours, and finally C9-HCI-3 resin with a viscosity of 3200 mPa·s and an -NCO content of 9% was obtained.

[0063] Table 3 Recipe of Example 3

[0064]

[0065]

[0066] Example 4:

[0067] S1. The C9-HCR reactant raw materials α-methylstyrene, indene, styrene and bisphenol A in Example 4 were placed in a four-necked flask containing xylene solvent at room temperature; the stirrer was started to disperse all the reaction materials evenly in the xylene solvent.

[0068] S2. The temperature of the reactor was controlled at 30 °C, and the initiator was slowly added dropwise while controlling the dropping rate of the initiator, and the initiator in the formula was added dropwise within 10 minutes.

[0069] S3. After the initiator was added dropwise, the reaction was carried out under the constant temperature condition of 30 °C, and the constant temperature time was controlled for 2.5 hours.

[0070] S4. After the reaction was completed, an appropriate amount of 10% Na2CO3 solution by mass was taken and added to the flask and stirred evenly, and then the temperature was raised to 70 °C for 30 minutes of alkali washing.

[0071] S5. After the alkalinity was completed, deionized water was added to the flask and heated to 80 °C for water washing, and then the water and oil were separated; the water washing and separation operations were repeated 4 times until the pH of the washing liquid was neutral, and then the upper oil-phase organic liquid was poured into the distillation flask.

[0072] S6. The washed resin organic liquid was poured into a weighed distillation flask, and the round-bottom flask was connected to the vacuum distillation device to check the airtightness of each ground glass joint of the device; the condensate water, vacuum pump and heating jacket switches were turned on respectively, and distillation was started. The vacuum degree was controlled at 0.06 MPa, the distillation temperature was 100 °C, and when there was no distillate in the system after 1 hour of distillation, the C9-HCR-4 resin product was obtained, and the viscosity, hydroxyl value, moisture content of the C9-HCR-4 resin were measured, and the yield of the C9-HCR-4 resin product was calculated.

[0073] S7. Take 100 grams of C9-HCR-4 resin, add dibutyltin dilaurate, start stirring, heat up to 70 °C, and then start adding dropwise MDI-50 was added dropwise within 30 minutes, and the reaction was carried out at a temperature of 70 °C for 3 hours. Finally, C9-HCI-4 resin with a viscosity of 2800 mPa·s and an -NCO content of 8% was obtained;

[0074] Table 4 Formulation of Example 4

[0075]

[0076] Table 5 Performance Parameter Table of C9-HCR and C9-HCI

[0077]

[0078] Comparison of Curing Performance of C9-HCI Resin-based Polyurethane Adhesive:

[0079] Under the condition of room temperature of 20 - 25 °C, C9-HCI resin, PMDI resin, and flame retardant were used to prepare a uniform polyurethane resin solution; a silicate solution was added to the above uniform polyurethane resin solution and mixed evenly to form a casting solution; part of the casting solution was taken to test the gel time; the remaining two-component polyurethane casting solution was injected into a mold and cast at room temperature, and the relevant mechanical properties were tested. In the C9-HCI resin-based polyurethane adhesive, PMDI is preferably PM-200 produced by Wanhua Chemical; the phosphorus-based flame retardant is preferably commercially available industrial product trichloropropyl phosphate (TCPP); the aqueous silicate solution is preferably commercially available water glass with a Baume degree of 50% and a modulus of 2.2 - 2.8.

[0080] For the C9-HCI resin-based polyurethane adhesive, its curing speed is characterized by measuring the gel time; the mechanical strength after curing is characterized by testing the flexural strength and flexural modulus of the casting body; the flexural strength after curing > 40 MPa, and the flexural modulus > 4000 Mpa.

[0081] Table 6 Performance Comparison Table of Polyurethane Adhesive

[0082]

[0083]

[0084] The beneficial effects of the present invention are as follows: From the flexural strength data of adhesives 1 - 6 in the above table and the polyurethane adhesive cured by the present invention, it can be seen that although the C9-HCR resin does not contain reactive -NCO reaction functional groups, the strength of the polyurethane adhesive prepared from it is still greater than that of the currently commercially available C9 hydrocarbon resin; and the C9-HCI resin containing -NCO can form a cross-linked structure with other components in the adhesive, so the strength of the adhesive prepared from C9-HCI is better.

[0085] From the comparison of adhesives 6, 7, 8, and 9, it can be seen that in the present invention, the adhesive strength is affected not only by the C9-HCR resin and C9-HCI resin, but also by other components in the adhesive and their addition ratios.

[0086] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of a C9 hydrocarbon resin-based polyisocyanate resin, characterized in that, The method comprises the following steps: Reacting a phenol-modified liquid hydrocarbon resin with a polyisocyanate at 60 - 80 °C for 2 - 6 hours to obtain the C9 hydrocarbon resin-based polyisocyanate resin, and the C9 hydrocarbon resin-based polyisocyanate resin has a structure as shown in Formula 1: where n is a positive integer from 1 to 5; where R1 is respectively selected as CH3 or H; R2 is respectively selected as H, CH3, -OH or R3 is The preparation method of the phenol-modified liquid hydrocarbon resin comprises the following steps: Reacting a hydroxyl-containing phenol monomer, a C9 aromatic olefin monomer and an initiator in a reaction medium at a temperature of 10 - 60 °C for 2 - 6 hours to obtain the phenol-modified liquid hydrocarbon resin, and the phenol-modified liquid hydrocarbon resin has a structure as shown in Formula 2: where n is a positive integer from 1 to 5; where R1 is respectively selected as CH3 or H; wherein R2 is respectively selected as H, CH3, -OH or The mass fraction of isocyanate groups in the C9 hydrocarbon resin-based polyisocyanate resin is 2 - 10%, the viscosity is 800 - 5000 mPa·s, the initiator is BF3·Et2O, and the dosage of the initiator accounts for 0.1 - 3% of the total amount of the hydroxyl-containing phenol monomer and the C9 aromatic olefin monomer. The hydroxyl value of the phenol-modified liquid hydrocarbon resin is in the range of 60 - 300 mgKOH / g, the viscosity is in the range of 500 - 3000 mPa·s, and the water content is controlled below 0.01%.

2. A polyurethane adhesive, characterized in that: The polyurethane adhesive comprises the C9 hydrocarbon resin-based polyisocyanate resin prepared by the preparation method according to Claim 1.

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