CN106946805A - Carbamate compound - Google Patents

Abstract

The invention provides a carbamate compound represented by formula (1), In formula (1), R ₁ , R ₂ and R ₃ are each independently -(CH ₂ ) _n -, n is an integer from 2 to 12, and X ₁ is the residue of caprolactone acrylate after removing one hydrogen on the hydroxyl group. group, X ₂ is _the residue of pentaerythritol triacrylate that removes one hydrogen on the hydroxyl group, and The urethane compound of the present invention functions as a bifurcating agent, can provide molded products with high melt tension, contributes to thinning processing, and improves production stability.

Description

carbamate compound

technical field

The present invention relates to a urethane compound, and more particularly to a urethane compound for use in the synthesis of branched copolymers with copolymerizable monomers.

Background technique

In recent years, thermoplastic resin has been widely used in different fields, such as household Electrical appliances, mechanical parts, office supplies, electronic components and the automotive industry, etc.

In general, thermoplastic resins can be processed by molding methods such as injection molding, extrusion molding, and blow molding. In addition, during specific processing and molding, the above-mentioned resin needs to be pressed into a sheet and then molded. In order to meet this requirement, the resin must have high melt strength (that is, increase the molecular weight of the resin) in order to maintain good thickness uniformity and dimensional stability during thermoforming or vacuum forming.

However, after increasing the molecular weight of the resin, it will cause disadvantages such as decreased fluidity, poor processability and reduced productivity. In order to improve this shortcoming, it is usually improved by adding a splitting agent. In the prior art, the branching agent added is a multifunctional reactive monomer, such as a divinyl compound or a polyvalent acrylate compound; Avoid the disadvantages of reduced fluidity and poor processability, but it is easy to cause crosslinking, which will cause the resin to adhere to the surface of the pipeline to form carbides, which will lead to unsmooth process operation and poor hue of the prepared resin.

To sum up, how to increase the degree of divergence to increase the melt tension of the resin, and at the same time contribute to thinner processing and improve production stability, is a subject that has long been in urgent need of breakthroughs for those familiar with this technical field.

Contents of the invention

The present invention provides a novel urethane compound, which is used to synthesize a branched copolymer with a copolymerizable monomer, so that the molded product has high melt tension, which is helpful for thinning processing and improving production stability.

The carbamate compound of the present invention is represented by formula (1),

In formula (1), R ₁ , R ₂ and R ₃ are each independently -(CH ₂ ) _n -, n is an integer from 2 to 12, and X ₁ is the residue of caprolactone acrylate after removing one hydrogen on the hydroxyl group. X2 is the residue of pentaerythritol triacrylate removing one _hydrogen on the hydroxyl group, and _X3 is the residue removing one hydrogen on the hydroxyl group of the hydroxyl-containing (meth)acrylate compound.

In an embodiment of the present invention, the hydroxyl-containing (meth)acrylate compound includes pentaerythritol triacrylate or caprolactone acrylate.

In one embodiment of the present invention, the urethane compound is obtained by reacting pentaerythritol triacrylate and caprolactone acrylate with a triisocyanate compound, and the triisocyanate compound is represented by formula (2),

In formula (2), R _a , R _b , and R _c are each independently -(CH ₂ ) _n -, and n is an integer of 2 to 12.

In one embodiment of the present invention, the carbamate compound is represented by formula (3) or formula (4),

In formula (3) and formula (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer from 2 to 12, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ are -(CH ₂ ) ₅ -.

In an embodiment of the present invention, in formula (3) and formula (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer of 2 to 10.

In an embodiment of the present invention, in formula (3) and formula (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer of 4-8.

In an embodiment of the present invention, in formula (3) and formula (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is 6.

In one embodiment of the present invention, a urethane compound is used to synthesize a branched copolymer with a copolymerizable monomer.

In an embodiment of the present invention, the copolymerizable monomer includes at least one selected from the group consisting of styrene-based monomers, acrylonitrile-based monomers and (meth)acrylate-based monomers.

In an embodiment of the present invention, the molar mass of the branched copolymer is in the range of 2×10 ⁵ g/mol to 3×10 ⁶ g/mol, and the average radius of rotation is 30 nm to 50 nm.

Based on the above, the carbamate compound provided by the present invention is suitable for polymer synthesis, and it is used for synthesizing with copolymerizable monomers at a molar mass of 2×10 ⁵ g/mol to 3×10 ⁶ g/mol The branched copolymer with an average radius of rotation of 30nm to 50nm has the function of a branching agent to make the molded product have high melt tension, which is helpful for thinning processing and improving production stability.

In order to make the above-mentioned features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail with reference to the accompanying drawings.

Description of drawings

Fig. 1 is the ¹ H-NMR spectrum of the carbamate compound of Synthesis Example 1;

Fig. 2 is the GPC collection of illustrative plates of the carbamate compound of synthetic example 1;

Fig. 3 is the ¹ H-NMR spectrum of the carbamate compound of Synthesis Example 2;

4 is a GPC chart of the carbamate compound of Synthesis Example 2.

detailed description

In the specification and claims of the present invention, the term "(meth)acrylate" means "acrylate and/or methacrylate".

The present invention provides a kind of carbamate (urethane) compound, it is represented by formula (1),

In formula (1), R ₁ , R ₂ and R ₃ are each independently -(CH ₂ ) _n -, n is an integer ranging from 2 to 12, and X ₁ is the hydroxyl group of caprolactone acrylate (caprolactone acrylate). One hydrogen residue, X ₂ is a residue of pentaerythritol triacrylate (pentaerythritol triacrylate) that removes one hydrogen on the hydroxyl group, and X ₃ is a residue that removes one hydrogen on the hydroxyl group of a hydroxyl-containing (meth)acrylate compound.

More specifically, in formula (1), R ₁ , R ₂ and R ₃ are each independently -(CH ₂ ) _n -, preferably, n is an integer from 2 to 10; more preferably, n is An integer of 4 to 8; most preferably n is 6.

The hydroxyl group-containing (meth)acrylate compound includes pentaerythritol triacrylate or caprolactone acrylate.

The urethane compound of the present invention is obtained by reacting pentaerythritol triacrylate and caprolactone acrylate with a triisocyanate compound.

The triisocyanate compound is represented by formula (2),

In formula (2), R _a , R _b , and R _c are each independently -(CH ₂ ) _n -, and n is an integer of 2 to 12.

More specifically, in formula (2), R _a , R _b , and R _c are each independently -(CH ₂ ) _n -, preferably, n is an integer from 2 to 10; more preferably, n is An integer of 4 to 8; most preferably n is 6.

Specific examples of the triisocyanate compound are represented by the following formulae.

Pentaerythritol triacrylate is represented by the following formula.

A specific example of caprolactone acrylate is represented by the following formula.

Specific examples of hydroxyl-containing (meth)acrylate compounds include, but are not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy methacrylate Propyl ester, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, methacrylic acid -3-hydroxybutyl acrylate, -4-hydroxybutyl acrylate, -4-hydroxybutyl methacrylate, dipropylene glycol acrylate, dipropylene glycol methacrylate, butylene glycol acrylate ester, butylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, polypropylene glycol methacrylate, polyethylene glycol- Polypropylene glycol-polypropylene glycol methacrylate, polyethylene glycol-1,4-butanediolmethacrylate (polyethylene glycol-1,4-butanediolmethacrylate), acrylic acid-2-hydroxy-3- 2-hydroxy-3-phenoxy-propylacrylate, pentaerythritol triacrylate and caprolactone acrylate. Preferably, the hydroxyl-containing (meth)acrylate compound is pentaerythritol triacrylate or caprolactone acrylate.

The carbamate compound of the present invention is preferably represented by formula (3) or formula (4),

In formula (3) and formula (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer from 2 to 12, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ are -(CH ₂ ) ₅ -.

More specifically, in formula (3) and formula (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, preferably, n is an integer from 2 to 10; more preferably, n is an integer from 4 to 8; most preferably, n is 6.

The urethane compound of the present invention is used to synthesize a branched copolymer with a copolymerizable monomer, wherein the copolymerizable monomer may comprise a styrene-based monomer, an acrylonitrile-based monomer, and (meth)acrylic acid At least one member of the group consisting of ester-based monomers. More specifically, the copolymerizable monomer is preferably a styrenic monomer. That is, the urethane compound of the present invention functions as a branching agent, can impart a high melt tension to a molded product, contribute to thinning processing, and improve production stability.

Specific examples of styrenic monomers may include, but are not limited to, styrene, α-methylstyrene, p-tert-butylstyrene, p-methylstyrene, o-methylstyrene, m-methylbenzene Ethylene, 2,4-dimethylstyrene, ethylstyrene, alpha-methyl-p-methylstyrene or bromostyrene. Preferably, the styrenic monomer is styrene, α-methylstyrene, or a combination thereof. The styrene-based monomer used in the present invention can be a single monomer or two or more monomers used in combination.

Acrylonitrile-based monomers can also be used alone or in combination, and acrylonitrile-based monomers include but are not limited to acrylonitrile or α-methacrylonitrile. Preferably, the acrylonitrile monomer is acrylonitrile.

Specific examples of (meth)acrylate-based monomers include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, polyethylene glycol diacrylate, methyl methacrylate, Ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, methacrylate 2 -Hydroxyethyl ester, glycidyl methacrylate, dimethylaminoethyl methacrylate, ethylene dimethacrylate, neopentyl dimethacrylate, and the like. Preferably, the (meth)acrylate monomers are butyl acrylate, methyl methacrylate and butyl methacrylate. The (meth)acrylate monomer used in the present invention may be a single monomer or two or more monomers used in combination.

Hereinafter, the above-mentioned carbamate compound proposed by the present invention will be described in detail through experimental examples. However, the following experimental examples are not intended to limit the present invention.

Experimental example

In order to prove that the urethane compound proposed by the present invention can be synthesized into a branched copolymer with a copolymerizable monomer, so as to make the molded product have high melt tension, the following experiment example is specially made.

Preparation of carbamate compounds

Synthesis Example 1

The carbamate compound of Synthesis Example 1 can be prepared by the following Reaction Scheme 1.

[Reaction scheme 1]

Y represents the residue of SR495B (caprolactone acrylate) with one hydrogen removed from the hydroxyl group.

1.9 parts by weight of MEHQ (Monomethyl ether hydroquinone), 600 parts by weight of HDT (trade name N3300, which is a trimer of hexamethylene diisocyanate (HDI), 1361 parts by weight of EB (Ethylene glycol monobutyl ether) and 1.9 parts by weight of DBDTL (di Dibutyltin dilaurate (Dibutyltin dilaurate)) was placed into a four-necked reaction flask, and stirred evenly to form a mixed solution. Afterwards, 757 parts by weight of SR495B (Caprolactoneacrylate) manufactured by Sartomer was slowly dropped into the mixed solution at room temperature, and the temperature was raised to 50° C. for 1 hour to react. Next, 514 parts by weight of PETIA (trade name EM235-1 (pentaerythritol triacrylate)) manufactured by Eternal Materials Co., Ltd. (Eternal Materials Co., Ltd.) was dissolved in 514 parts by weight of EB, and then dropwise After the reaction was completed, the temperature was lowered to room temperature, and the resultant was filtered out to obtain a carbamate compound.

FIG. 1 is a ¹ H-NMR spectrum of the carbamate compound of Synthesis Example 1. FIG. The results of ¹ H-NMR (hydrogen nuclear magnetic resonance) were measured using a nuclear magnetic resonance spectrometer Ultrashield 400 MHz manufactured by Bruker. As shown in Figure 1, the H (3.5ppm) signal of the SR495B functional group OH disappeared, and the H (3.2ppm) signal of HDT shifted, so it was confirmed that the reaction was progressing.

FIG. 2 is a GPC chart of the carbamate compound of Synthesis Example 1. Using Gel Permeation Chromatography (GPC) manufactured by Waters (Waters), equipped with differential refractive index detector (Waters RI-2414) and ultraviolet visible light detector (Waters PDA-2996) for analysis and determination, analysis conditions Column: MZ-Gel Sdplus linear 5μm 300×8.0mm, mobile phase: THF (flow rate 0.5ml/min). As shown in FIG. 2 , the low molecular weight disappeared and the high molecular weight appeared, so it was confirmed that the reaction proceeded.

Synthesis example 2

The carbamate compound of Synthesis Example 2 can be prepared by the following Reaction Scheme 2.

[Reaction scheme 2]

Y represents the residue of SR495B (caprolactone acrylate) with one hydrogen removed from the hydroxyl group.

2 parts by weight of MEHQ (hydroquinone monomethyl ether), 600 parts by weight of HDT (trade name N3300), 1036.5 parts by weight of EB (ethylene glycol monobutyl ether) and 2 parts by weight of DBDTL (dibutyltin dilaurate) were put into a four-necked reaction flask and stirred evenly to form a mixed solution. After that, 432.5 parts by weight of SR495B (Caprolactone acrylate) manufactured by Sartomer was slowly dropped into the mixed solution at room temperature, and the temperature was raised to 50° C. for 1 hour to react. Then, 955 parts by weight of PETIA (trade name EM235-1 (pentaerythritol triacrylate)) was dissolved in 955 parts by weight of EB, then dropped into the reaction, then heated to 75 ° C for 5 hours, after the reaction, the temperature After cooling down to room temperature, the resultant was filtered out to obtain a carbamate compound.

FIG. 3 is a ¹ H-NMR spectrum of the carbamate compound of Synthesis Example 2. FIG. As shown in Figure 3, the H (3.5ppm) signal of the SR495B functional group OH disappeared, and the H (3.2ppm) signal of HDT shifted, so it was confirmed that the reaction was proceeding.

4 is a GPC chart of the carbamate compound of Synthesis Example 2. As shown in FIG. 4 , the low molecular weight disappeared and the high molecular weight appeared, so it was confirmed that the reaction proceeded.

The ¹ H-NMR spectrum in FIG. 3 is measured in the same manner as the ¹ H-NMR spectrum in FIG. 1 , and the GPC spectrum in FIG. 4 is measured in the same manner as the GPC spectrum in FIG. 2 , so details will not be described here.

Synthesis of Copolymer

Example 1

Add 150ppm of 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane (TX-29A) to 92.4 parts by weight of styrene monomer and 7.4 parts by weight of ethylbenzene , 250ppm of n-dodecylmercaptan (n-Dodecylmercaptan) and 110ppm of 3-(3',5'-bis-tert-butyl-4'-hydroxyphenyl) n-octadecyl propionate ( Octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate) (IX-1076, manufactured by CIBA) and 220ppm tris-(2,4-bis-tert-butyl-phenyl ) phosphoric acid ester (tri-(2,4-di-t-butyl-phenyl) phosphate) (P-168), add the carbamate compound of Synthetic Example 1 of 650ppm and react, and the reaction condition is: every The flow rate of 40 liters per hour is pumped into three columnar flow reactors connected in series with a capacity of 110 liters. The reaction inlet temperatures are kept at 115°C, 130°C, and 150°C, and the final conversion rate is 80% by weight. The heater is heated, and the devolatilization equipment operated under a vacuum of 15torr removes unreacted monomers and inert solvents, and the copolymer is obtained after being extruded by the extrusion equipment.

Example 2

The synthesis method is the same as in Example 1, except that 500 ppm of the carbamate compound of Synthesis Example 2 is added for reaction instead of 650 ppm of the carbamate compound of Synthesis Example 1 for reaction.

Reference example 1

The synthesis method is the same as in Example 1, except that the carbamate compound in Synthesis Example 1 or Synthesis Example 2 is not added for reaction.

Evaluation: Determination of the average radius of gyration of copolymers

For the copolymers of Example 1, Example ² and Reference Example ¹ , the average radius of rotation ( average radius of gyration) determination. Gel Permeation Chromatography (GPC) manufactured by Waters Corporation is used in series with a multi-angle laser light scattering instrument (multi-angle laserlight scattering; MALLS) and model DAWN8+ manufactured by Wyatt Technology Corporation The viscometer (viscometer) of ViscoStar-II was used for measurement, and the analysis conditions were column: MZ-Gel Sdplus linear 5 μm 300×8.0 mm, mobile phase: THF (flow rate 0.5 ml/min). The assay results are shown in Table 1 below.

[Table 1]

It can be known from the above Table 1 that during the synthesis of the copolymer of Comparative Example 1, the carbamate compound of Synthesis Example 1 or Synthesis Example 2 was not added for reaction. Therefore, the molar mass is 2×10 ⁵ to In the range of 3×10 ⁶ g/mol, the value of the average radius of rotation is small (19.4nm), which means that the divergence effect is poor.

In contrast, Example 1 and Example 2 use the carbamate compound proposed by the present invention to react to synthesize a copolymer. Since the carbamate compound of the present invention has the function of a splitting agent, it can be combined with a copolymer Polymerized monomers are synthesized into branched copolymers. Therefore, in the range of molar mass from 2×10 ⁵ to 3×10 ⁶ g/mol, the average gyration radii of the copolymers synthesized in Example 1 and Example 2 are respectively 35.2nm and 42.0nm (ie, the average radius of rotation is 30nm to 50nm), the larger the value of the average radius of rotation, the better the divergence effect.

In summary, the urethane compound proposed by the present invention is used to synthesize branched copolymers with copolymerizable monomers, wherein the copolymerizable monomers may include styrene-based monomers, acrylonitrile-based monomers, At least one of the group consisting of monomers and (meth)acrylate monomers. The synthesized branched copolymer has a molar mass in the range of 2×10 ⁵ g/mol to 3×10 ⁶ g/mol, an average radius of rotation of 30nm to 50nm, and the branching effect is good. Therefore, the urethane compound of the present invention functions as a branching agent, can impart high melt tension to molded products, contribute to thinning processing, and improve production stability.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. scope.

Claims (10)

1. a kind of carbamate compounds, it is characterised in that the carbamate compounds represent by formula (1),

In formula (1), R₁、R₂And R₃It is each independently-(CH₂)_n-, n is 2 to 12 integer, X₁For going for caprolactone The residue of a hydrogen, X on hydroxyl-removal₂For the residue for removing a hydrogen on hydroxyl-removal of pentaerythritol triacrylate, X₃For hydroxyl (methyl) acrylate compounds the residue for removing a hydrogen on hydroxyl-removal.

2. carbamate compounds according to claim 1, it is characterised in that (methyl) acrylic acid of the hydroxyl Ester compounds include pentaerythritol triacrylate or caprolactone.

3. carbamate compounds according to claim 1, it is characterised in that the carbamate compounds be by React and obtain, the triisocyanate with tri-isocyanate compound comprising pentaerythritol triacrylate and caprolactone Formula (2) expression,

In formula (2), R_a、R_b、R_cIt is each independently-(CH₂)_n-, n is 2 to 12 integer.

4. carbamate compounds according to claim 1, it is characterised in that the carbamate compounds are by formula (3) or formula (4) represent,

In formula (3) and formula (4), R₄、R₅、R₆、R₁₁、R₁₂And R₁₃It is each independently-(CH₂)_n-, n is 2 to 12 integer, R₇、 R₈、R₉、R₁₀、R₁₄And R₁₅For-(CH₂)₅-。

5. carbamate compounds according to claim 4, it is characterised in that in formula (3) and formula (4), R₄、R₅、 R₆、R₁₁、R₁₂And R₁₃It is each independently-(CH₂)_n-, n is 2 to 10 integer.

6. carbamate compounds according to claim 4, it is characterised in that in formula (3) and formula (4), R₄、R₅、 R₆、R₁₁、R₁₂And R₁₃It is each independently-(CH₂)_n-, n is 4 to 8 integer.

7. carbamate compounds according to claim 4, it is characterised in that in formula (3) and formula (4), R₄、R₅、 R₆、R₁₁、R₁₂And R₁₃It is each independently-(CH₂)_n-, n is 6.

8. carbamate compounds according to claim 1, it is characterised in that the carbamate compounds are used for Difference shape copolymer is synthesized with copolymerizable monomer.

9. carbamate compounds according to claim 8, it is characterised in that the copolymerizable monomer is included and is selected from At least one in the group be made up of styrenic monomers, acrylic monomer and (methyl) acrylic ester monomer.

10. carbamate compounds according to claim 8, it is characterised in that the difference shape copolymer mole Quality is 2 × 10⁵G/mol to 3 × 10⁶G/mol scope, average radius of gyration is 30nm to 50nm.