TW202124509A - Developments of biomass aqueous pu resin with high resilience and formulations thereof - Google Patents

Abstract

The present invention relates to polymeric materials, in particular an aqueous biomass polyurethane emulsion, and especially relates to using, as polymerization monomers, a polyester polyol prepared by polymerization monomers comprising 2-methylbutanedioc (2-mSA). The presnet invention also relates to methods of preparing the aqueous biomass polyurethane emulsion.

Description

High backwash elastic biological waterborne PU resin and formulation development technology

The present invention relates to the field of polymer materials, in particular to an aqueous biogenic polyurethane emulsion. The present invention also relates to a method for preparing an aqueous biogenic polyurethane emulsion.

In the past, only material performance, properties, and costs were emphasized in materials. With the rise and promotion of global sustainability awareness, industries in various fields have begun to consider the impact and impact of materials on the environment from the perspective of life cycle. For this reason, brand owners in all fields of the world have plans or are developing the innovation and application of biomaterials.

Among the organic acids, itaconic acid has been listed as one of the twelve biochemical compounds with the most potential for development by the U.S. Department of Energy. In 2015, the global annual demand for itaconic acid was 5,000 tons, with an output value of about 4 billion Taiwan dollars. It is estimated that the global annual demand for itaconic acid in 2023 will be 90,000 tons, with an output value of approximately NT$6.1 billion. Itaconic acid has two carboxyl groups and one methylene group, also known as methylene succinic acid, methylene succinic acid (2-Methylidenebutanedioic acid) or methylene butanedioic acid (Methylene Butanedioic Acid), which is white crystals. Special odor, melting point is about 162~164°C, density is 1.63 g/cm ³ , it can be polymerized in itself or with other monomers, and it is easily soluble in water, ethanol and other solvents. It has a wide range of applications and can be used for synthesis. As raw materials for resins, plastic materials, rubber, synthetic fibers, crosslinking agents, emulsifiers, ion exchange resins, polymer chelating agents and surfactants, the international market for itaconic acid is promising.

For example, more than 90% of the current bag and box industry uses solvent-based polyurethane (PU) in synthetic resins. For this reason, for the development of environmentally friendly water-based PU resins for coating with high backlash elasticity, abrasion resistance, water pressure resistance, stick resistance and good hand feeling and mechanical strength that can meet the industrial scale and high-end bags and boxes, and at the same time, it needs to comply with the brand business. In the future, the trend of product materials, products that meet the minimum standards of bio-based content for bioassay, are still in demand, in order to facilitate entry into the international, especially the US market, and enhance the competitiveness of domestic related industries.

Polyols required for the preparation of PU generally use dicarboxylic acids and diols through condensation esterification polymerization to prepare polyester polyols. Bio-based diols are already available on the market, but bio-based dicarboxylic acids are very rare. However, polyols belong to the soft segment in the water-based PU structure. Therefore, if you use existing bio-based diols with non-bio-based dicarboxylic acids, you want to pass the USDA bio-quality certification of ≧25% of bio-components. The need to use a high amount of polyol results in the mechanical properties of the final PU being more viscous and fluid, which cannot meet the high viscoelastic requirements of water-based PU, which greatly limits the development and application of bio-based water-based PU. In addition, although itaconic acid is a bio-based dicarboxylic acid, if itaconic acid is directly applied to the synthesis of polyester polyols, the double bonds of unhydrogenated itaconic acid are prone to free radical polymerization at high temperatures, making it difficult Control the molecular weight and quality of synthetic polyester polyols, and the double bonds are easy to cause yellowing, cracking, poor film-forming properties and poor adhesion to the substrate or substrate, etc., and further modification or grafting is required. Synthetic reaction, so it is not suitable for large-scale production.

Therefore, there is still a need for development of biomass water-based PU resins.

In order to solve the aforementioned problems, the present invention uses itaconic acid to produce 2-mSA through hydrogenation, which still contains a dicarboxylic acid (-COOH) structure, and esterifies with a diol to prepare polyols. The reaction is relatively stable and easier to control. For example, molecular weight control and molecular weight distribution are more accurate, and the biomass content of polyols with different molecular weights is about 33~54% under different reactant ratios. This not only greatly exceeds the USDA bio-based content standard (≥ 25%), and because it can already exceed the USDA bio-based content standard, the dicarboxylic acid structure of 2-mSA can be used to design the block ester/ether copolymer soft The chain segment structure enables the development of bio-based water-based PU products to have a wider structural ratio adjustment space, and more diversified product development and applications can be developed.

To achieve the above purpose, the present invention uses the most suitable bio-polyester polyol, as well as diols, diamines (influencing the molecular weight, melting point and tensile strength of water-based PU) and hydrophilic chain extenders (which can increase the prepolymer The hydrophilicity enables it to be effectively and evenly dispersed in water. Adjust the addition amount to discuss the stability of the synthesized emulsion and particle size), synthesize a unique bio-polyester polyol, block formula composition of soft and hard segments, and NCO/OH The proportion of control, and optimize the process conditions.

Preliminary experiments, using itaconic acid without hydrogenation reaction and hydrogenated biomass 2-mSA, respectively, mixed with ethylene glycol (1,2-EG) and 1,4-butanediol (1,4-BG) And tin oxide catalyst, polycondensation reaction at 180℃~190℃ for 3hrs, after removing impurities in the system under vacuum, synthesize bio-based polyester polyol. The results show that itaconic acid without hydrogenation reaction is prone to free radical polymerization reaction under high temperature esterification reaction because it contains unsaturated double bonds, and it is very easy to produce self-crosslinking gel, and it is impossible to make polyester polyols smoothly. ; The hydrogenated biomass 2-mSA can avoid the above-mentioned free radical polymerization and cross-linking reaction, resulting in a unique three-dimensional structure with Mw=2,150, OH value=55 mg KOH/g, and acid value <0.8 mg KOH/g Structured polyester polyol. Therefore, the hydrogenation reaction technology is very important for subsequent PU synthesis applications.

In order to solve the problem of water-based PU resin that can pass the bio-component ≧25% USDA bio-certification, the 2-mSA bio-dicarboxylic acid with a unique side chain structure has the stereo effect of the side chain methyl group, so that the soft segment has more Good flexibility, and because the side chain methyl group increases the intermolecular distance, the steric hindrance becomes larger and the molecular chain regularity is reduced. In addition to not affecting the Tg glass transition temperature, it lowers the Tm melting point and gives it a 2- mSA synthetic PU has a unique high backlash elasticity, and then develops a differentiated biological waterborne PU resin with high backlash elasticity and high viscoelasticity.

The primary purpose of the present invention is to invent a high backwash elastic biogenic waterborne PU resin, and to provide a polyisocyanate, biopolyester polyol, polypolyol, diol, diamine, hydrophilic chain extender, and Solvent-based biological water-based PU resin.

Polyurethane

In a specific example, the high backlash elastic biomass waterborne PU resin provided by the present invention has a biomass content of at least 25%, preferably at least 30%, more preferably at least 45%, more preferably at least 65% .

In a specific example, the hydrolysis resistance of the high-backlash elastic biological waterborne PU resin provided by the present invention is at least 75%, preferably at least 80%, and more preferably at least 85% according to the ISO 1419:1995 standard.

In a specific example, the weight-average molecular weight of the high backlash elastic biomass water-based PU resin provided by the present invention is preferably 40,000 to 60,000 g/mol, more preferably 45,000 to 55,000 g/mol, most preferably 47,000 to 53,000 g/mol.

In a specific example, the water-based PU resin provided by the present invention has a yellowing resistance level of 4 or higher as measured in accordance with ASTM D1148.

In a specific example, the high backlash elastic biomass waterborne PU resin provided by the present invention has an elastic recovery rate of at least about 85%, preferably 90%, and more preferably 95%.

Polyisocyanate

In the preparation of the aqueous bio-PU resin of the present invention, suitable polyisocyanates preferably include diisocyanates, such as (cyclo)aliphatic diisocyanates, aromatic diisocyanates and/or araliphatic diisocyanates. Examples of (cyclo)aliphatic diisocyanates include (but are not limited to) 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,12-dodecamethylene diisocyanate Isocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), diphenylmethane 4,4-diisocyanate (MDI), dicyclohexyl Methane diisocyanate (HMDI), 1,6-hexamethylene diisocyanate (HDI), methyl cyclohexyl diisocyanate (HTDI), etc. Examples of aromatic diisocyanates include, but are not limited to, examples of toluene diisocyanate (TDI), naphthalene-1,5-diisocyanate (NDI), polymethylene polyphenyl isocyanate (PAPI), and araliphatic diisocyanate Including (but not limited to) xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI); and mixtures of any of the foregoing components. The preferred polyisocyanates are isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), 1,6-hexamethylene diisocyanate (HDI), biscyclohexylmethane diisocyanate (HMDI), diphenylmethane 4,4-Diisocyanate (MDI), toluene diisocyanate (TDI) or any mixture thereof; if the end product has yellowing resistance and light stability requirements, it can be aliphatic diisocyanate. If the end product emphasizes high tensile strength, you can Aromatic diisocyanates are the main ones. Because aromatic polyisocyanates have rigid aromatic rings, their mechanical properties are better than aliphatic polyisocyanates.

According to one aspect of the present invention, based on the total solid content of the biomass water-based PU resin, the content of the polyisocyanate is 2 to 30 wt%, such as: 2 wt%, 4 wt%, 6 wt%, 8 wt% , 10% by weight, 12% by weight, 14% by weight, 16% by weight, 18% by weight, 20% by weight, 22% by weight, 24% by weight, 26% by weight, 28% by weight, or 30% by weight, preferably 5 To 25% by weight, particularly preferably 10 to 20% by weight.

Bio-polyester polyol

Among the bio-waterborne PU resins of the present invention, bio-polyester polyols are specially developed by Coating Precision Materials Co., Ltd. for bio-polyester polyols.

Polyester polyols are prepared by esterification reaction of polyols and polyacids. The following describes the characteristics of the reactive monomers and polyester polyols.

Polyol

Polyol refers to a hydrocarbon derivative with two or more hydroxyl groups (-OH). In the present invention, for example, alkyl polyols, unsaturated or aromatic polyols can be used. Biomass polyols can also be used. As a reactive monomer of polyester polyols. It can also clearly indicate the number of hydroxyl groups carried by hydrocarbon derivatives, such as diols, triols, etc.

When preparing the polyester polyol used in the present invention, it is preferable to use (cyclo)alkyl glycol as the reactive monomer. Examples of polyols include (but are not limited to) diols with carbon numbers 2-12 and 36, such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 2-methyl-1, 3-propanediol, hexanediol, dipropylene glycol, butyl ethyl propylene glycol, diethyl pentanediol, 3-methyl 1,5-pentanediol, 1,4-cyclohexyl dimethanol, cyclohexane diol , Dodecanediol, spirodiol, trimethylpentanediol, pentanediol, hydroxypivalate neopentyl glycol monoester, ethyl hexanediol, dodecanediol, etc., p-benzene One or more of diphenol dihydroxyethyl ether, resorcinol dihydroxyethyl ether, trimethylolpropane, glycerin, trimethylolethane, 1,2,6-hexanetriol, and the like. In a specific example of preparing the polyester polyol used in the present invention, ethylene glycol and butylene glycol are used as reactive monomers; in a specific example of preparing the polyester polyol used in the present invention, propylene glycol is used as Reaction monomer.

Polyacid

Polyacids refer to hydrocarbon derivatives with two or more carboxyl groups (-COOH). When preparing the polyester polyol used in the present invention, for example, alkyl polybasic acid, unsaturated or aromatic polybasic acid can be used. As a reactive monomer of polyester polyols. It can also clearly indicate the number of carboxyl groups carried by hydrocarbon derivatives, such as dibasic acid, tribasic acid, etc.

When preparing the polyester polyol used in the present invention, it is preferable to use an alkyl dibasic acid as the reactive monomer, which includes at least 2-methylsuccinic acid (2-mSA) as the reactive monomer, because 2- The structure of mSA has a side chain methyl group, which exhibits a three-dimensional effect, so that the soft segment of the polyurethane exhibits better flexibility. In addition, because the side chain methyl groups increase the distance between molecules, the steric hindrance becomes larger and the regularity of the molecular chain is reduced. Therefore, this structure not only does not damage the Tg, but also reduces the Tm, giving polyester polyols unique properties when applied to polyurethane. It can also be used in combination with other biomass monomers, such as biomass succinic acid.

Other dibasic acids with carbon numbers from 4 to 36 can be further used as reactive monomers, examples include (but are not limited to) succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Sebacic acid, undecanedioic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride; 1,4-cyclohexanedicarboxylic acid, octadecane Unsaturated fatty acid dimer, maleic anhydride, etc. In a specific example of preparing the polyester polyol used in the present invention, based on the total moles of reactant monomers used, at least 30 mol% of 2-mSA is used, and preferably at least 32 mol% of 2-mSA is used. mSA, preferably at least 40 mol% 2-mSA. In one specific example of the polyester polyol used in the present invention, based on the total moles of the polyacid monomers used therein, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol% is used. mol% 2-mSA or only 2-mSA is used as the reactive monomer of polyacids. Anhydrides or esters formed by the aforementioned acids can also be used as the reaction monomer.

characteristic

The polyester polyol used in the present invention has a high biomass content and meets today's requirements for sustainable development. The biomass content is >30, preferably >40, more preferably >50, for example, within a reasonable range composed of the following endpoints: 30, 40, 50, 60, 70, 80, 90, or 100. In a specific aspect of the present invention, the biomass content of the polyester polyol is 30-100, preferably 50-100, more preferably 80-100. The relevant international testing instruments for the content of biomass materials include proportional counters, liquid scintillation counters, and accelerator mass spectrometers. The test target material is the carbon 14 (14C) isotope in the sample. The content of the biomass carbon source is calculated after comparing with the standard value, namely Is the biomass content.

Preparation method of polyester polyol with high biomass content

The manufacturing method of the polyester polyol used in the present invention includes reacting 2-methylsuccinic acid with a diol and optionally further added dibasic acid.

In a specific example of preparing the polyester polyol used in the present invention, the method for preparing a polyester polyol with high biomass content includes at least the following steps: (1) Add alkyl polyol, alkyl polyacid and antioxidant system to the reactor; (2) After the reaction is carried out at a temperature not higher than 160°C in a stable gas environment, the reaction temperature is increased to 180~230°C to continue the reaction; (3) When the acid value is lower than the first target value, apply vacuum to the reactor and allow the reaction to continue; (4) The reaction is completed when the acid value is lower than the second target value; Wherein the alkyl polybasic acid contains at least 2-methylsuccinic acid, and the antioxidant system contains at least two antioxidants.

In a specific example of preparing the polyester polyol used in the present invention, the stable gas in step (2) includes nitrogen, inert gas and the like. In a specific example of the present invention, the reaction of step (2) further includes the use of a catalyst. Examples include (but are not limited to) tin catalysts (such as T-9 catalysts, T-12 catalysts), titanium catalysts (such as TBT), and bismuth catalysts. One or more of metal catalysts such as catalysts and zinc catalysts.

In a specific example of preparing the polyester polyol used in the present invention, the antioxidant system includes a composite antioxidant of phosphite and hindered amine. Examples of phosphite antioxidants may be antioxidants 168, 618, 626. An example of the hindered amine complex antioxidant may be antioxidant 5057.

In a specific example of preparing the polyester polyol used in the present invention, the reaction of step (2) is maintained at not higher than 160°C, 130 to 150°C, preferably 135 to 145°C, more preferably The reaction is carried out at a temperature of 138 to 142°C or about 140°C, or the reaction is carried out at a temperature within a reasonable range composed of the aforementioned numerical range for 0.5 to 5 hours, preferably 0.5 to 3 hours, more preferably 1 to 2 hours, if The reaction time is too short, the reaction of acid and alcohol is not complete, and the monomer remains too much. Due to the poor heat resistance of the monomer, the color of the finished product will be poor, and the reaction time will be too long, which will cause the overall synthesis reaction time to lengthen, and the catalyst will vary with the reaction time. Poor performance makes it difficult to decrease the acid value; then increase the reaction temperature to 180-230°C, preferably at a temperature of 200-230°C. Without being limited by theory, it is known that because 2-methylsuccinic acid contains side groups, the reaction rate may be slower and the monomer has poor heat resistance, so the reaction is carried out at a lower temperature first; if it is directly higher than 180° C reacts, and the problem of color depth is easy to occur. In addition, the content of iron ions in 2-methylsuccinic acid obtained from biomass sources is usually high, so the color of polyester polyols prepared from it is likely to be higher than that of dibasic acids from petrochemical sources.

In a specific example of preparing the polyester polyol used in the present invention, the 2-methylsuccinic acid-containing biomass polyester polyol can be used to prepare a polyester polyol with a weight average molecular weight of 500 to 6000.

In a specific example of preparing the polyester polyol used in the present invention, the first target value of step (3) is less than 30 mgKOH/g, preferably less than 25 mgKOH/g, more preferably less than 20 mgKOH/g. In a specific example of the present invention, the second target value of step (4) is lower than 1 mgKOH/g, preferably lower than 0.8 mgKOH/g, more preferably lower than 0.5 mgKOH/g. In a specific example of the present invention, the vacuum condition of step (3) may be <60 torr (vacuum degree> -700 torr)

The polyester polyol with high biomass content used in the present invention also meets the chromaticity specifications required by the industry. In a specific aspect of the present invention, the APHA chromaticity exhibited by the polyester polyol is not higher than 30, preferably Not higher than 20, more preferably not higher than 15.

In a specific aspect of the polyester polyol used in the present invention, its weight average molecular weight ranges from 500 to 6,000, preferably from 800 to 5500, more preferably from 1000 to 4500, for example: 600, 700, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400, 3600, 3800, 4000, 4200, 4400, 4600, or 4800, preferably 1,000 to 4,000. Since polyester polyol can be used as the soft segment part in the synthesis of polyurethane, and the present invention uses polyester polyol with high biomass content, if the molecular weight of polyester polyol is too high, the proportion in the polyurethane will be high, which may lead to polyurethane The degradation rate is too fast, and it is not easy to be used in market products; if the molecular weight of polyester polyol is too low, the proportion of soft segment is low, which may cause the polyurethane to be too hard and inelastic. Therefore, in a specific example of preparing the polyester polyol used in the present invention, the synthetic formula is adjusted so that the molecular weight of the prepared polyester polyol with high biomass content falls within 1000~4000, making it easier to prepare products that meet market demand (High elasticity, high toughness, high backlash elasticity), and the maintenance rate of physical properties can reach more than three years.

In a specific aspect of the polyester polyol used in the present invention, the acid value range of the high biomass content polyester polyol is <2 KOH/g, preferably <1 KOH/g, more preferably <0.5 KOH /g. If the acid value is too high, it is easy to hydrolyze. For example, if the acid value is higher than 2, the hydrolysis resistance and reactivity will be poor, and it may be necessary to add a hydrolysis resistance agent to improve the hydrolysis resistance.

In a specific aspect of the polyester polyol used in the present invention, the hydroxyl value of the high biomass content polyester polyol ranges from 15 to 220 KOH/g, preferably 20 to 140 KOH/g, more preferably 28 ~100 KOH/g.

According to one aspect of the present invention, the weight average molecular weight of the biomass polyester polyol is 600 to 6,000, such as: 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400, 3600, 3800, 4000, 4200, 4400, 4600, 4800, 5000, 5200, 5400, 5500, 5600, 5800 or 6000, preferably 1,000 to 4,000 g/mol

According to one aspect of the present invention, the biomass content of the biomass polyester polyol is 30 to 100 mol%, such as: 30, 40, 50, 60, 70, 80, 90, or 100 mol%, or the foregoing Any reasonable range formed by the endpoints is preferably 50 to 80 mol%.

According to one aspect of the present invention, based on the total solid content of the biomass water-based PU resin, the content of the biomass polyester polyol is 40 to 90% by weight, such as 40% by weight, 45% by weight, and 50% by weight , 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, or 90% by weight, preferably 50 to 85% by weight, particularly preferably 60 to 80% by weight %.

Polypolyol

In the preparation of the biomass water-based PU resin of the present invention, suitable polypolyols may include polyester polyols, polylactone polyols, polyether polyols, polycarbonate polyols, polythioether polyols, and polyethers. Hybrid polyol with polyester, and any mixtures thereof. The polypolyol preferably includes polyethylene glycol, polypropylene oxide glycol, polytetrahydrofuran ether glycol, polybutylene succinate, polyhexylene adipate, and polybutylene adipate , Polyethylene glycol butylene adipate, polypropylene carbonate diol, or any mixture thereof, can be selected according to the characteristics of different finished products.

According to one aspect of the present invention, the weight average molecular weight of the polypolyol is 600 to 6,000, such as 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400 , 3600, 3800, 4000, 4200, 4400, 4600, 4800, 5000, 5200, 5400, 5500, 5600, 5800 or 6000, preferably 1,000 to 4,000 g/mol.

According to one aspect of the present invention, based on the total solid content of the biomass water-based PU resin, the content of the polypolyol is 0-50% by weight, such as: 0% by weight, 5% by weight, 10% by weight, 15% by weight %, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, or 50% by weight, preferably 5 to 40% by weight, and particularly preferably 10 to 30% by weight.

catalyst

In the preparation of the biomass water-based PU resin of the present invention, a catalyst may be additionally used as needed. Examples of catalysts suitable for the biomass water-based PU resin of the present invention include (but are not limited to) tertiary amine catalysts, (organo) tin catalysts, non-tin metal compound catalysts (such as titanium catalysts, bismuth catalysts, zinc catalysts) Catalyst, etc.), and any mixtures thereof. It preferably includes stannous octoate or dibutyltin dilaurate.

Regarding one aspect of the present invention, based on the total solid content of the biomass water-based PU resin, the content of the catalyst is 0 to 200 wt ppm, such as: 10 wt ppm, 20 wt ppm, 30 wt ppm, 40 wt ppm, 50 weight ppm, 60 weight ppm, 70 weight ppm, 80 weight ppm, 90 weight ppm, 100 weight ppm, 110 weight ppm, 120 weight ppm, 130 weight ppm, 140 weight ppm, 150 weight ppm, 160 weight ppm, 170 weight ppm ppm, 180 weight ppm, or 190 weight ppm, preferably 0 to 150 weight ppm, particularly preferably 0 to 100 weight ppm.

Small molecule chain extender

In the preparation of the biogenic water-based PU resin of the present invention, a small molecule chain extender may be additionally used as needed. According to one aspect of the present invention, examples of the small molecule chain extender include (but are not limited to) ethylene glycol, hexanediol, ethylene diamine, hexamethylene diamine, phenylenediamine, diethanolamine, polyoxypropylene triamine , Diethylene triamine, isophorone diamine, m-xylylenediamine, methyldiethanolamine, and any mixtures thereof.

According to one aspect of the present invention, based on the total solid content of the biomass water-based PU resin, the content of the small molecule chain extender is 0.1 to 20% by weight, such as: 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight %, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, or 19% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight.

Other hydrophilic chain extenders

In the preparation of the aqueous bio-PU resin of the present invention, a hydrophilic chain extender may be used as needed, but preferably does not contain a sulfonate functional polyether glycol type hydrophilic chain extender. According to one aspect of the present invention, examples of the hydrophilic chain extender include (but are not limited to) dimethylol propionic acid, dimethylol butyric acid, dihydroxy half ester, sodium ethylenediaminoethanesulfonate, two Sodium aminobenzene sulfonate, diaminopropionic acid, diaminobutyric acid, and any mixtures thereof.

Regarding one aspect of the present invention, based on the total solid content of the biomass water-based PU resin, the content of the other hydrophilic chain extender is 0.1 to 20% by weight, such as: 0.2% by weight, 0.3% by weight, 0.4% by weight , 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8 % By weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, or 19% by weight, preferably It is 0.5 to 15% by weight, particularly preferably 1 to 10% by weight.

Crosslinking agent

In the preparation of the water-based bio-PU resin of the present invention, a cross-linking agent may be used as needed to increase the cross-linking density and increase the hydrolysis resistance of the water-based polyurethane emulsion. According to one aspect of the present invention, examples of the crosslinking agent include (but are not limited to) aliphatic isocyanate, polyaziridine, water-based epoxy crosslinking agent, carbamido crosslinking agent, melamine- Formaldehyde resin (melamine), and any mixtures thereof.

Regarding one aspect of the present invention, based on the total weight of the biomass water-based PU resin, the content of the crosslinking agent is 0 to 20% by weight, such as: 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5 Weight%, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight , 18% by weight, or 19% by weight, preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight.

Solvent

Solvents suitable for the biogenic water-based PU resin of the present invention include water and water-miscible solvents. Preferably, the solvent consists essentially of water. Examples of water-miscible solvents include (but are not limited to) ketones, amides, etc., such as acetone, methyl ethyl ketone, N,N-dimethylformamide, N-methylpyrrolidone or any mixture thereof; These solvents can provide effects such as enhancing the solubility of the components and reducing the viscosity of the prepolymer. Regarding one aspect of the present invention, based on the total weight of the biomass water-based PU resin, the solvent content is 55 to 80% by weight, such as: 56% by weight, 58% by weight, 60% by weight, 62% by weight, 64% by weight %, 66% by weight, 68% by weight, 70% by weight, 72% by weight, 74% by weight, 76% by weight, or 78% by weight, preferably 60 to 75% by weight, particularly preferably 65 to 70% by weight.

According to a preferred aspect of the present invention, based on the total weight of the biomass water-based PU resin, the methyl ethyl ketone, acetone, N,N-dimethylformamide and/or N-methyl contained in the solvent The content of pyrrolidone is 40% by weight or less, such as: 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight % Or less, 5% by weight or less, or 1.0% by weight or less, preferably 30% by weight or less, more preferably completely free of any acetone, N,N-dimethylformamide and/ Or N-methylpyrrolidone.

Therefore, the biological water-based PU resin of the present invention can at least exhibit the following effects: A. Water-based PU resin that can pass the biological component ≧25% USDA certification. B. It is better to use 2-mSA biodicarboxylic acid with a unique side chain structure, which has the stereo effect of the side chain methyl group, so that the soft segment has better flexibility, and the side chain methyl group increases the intermolecular distance , To increase the steric hindrance, reduce the regularity of the molecular chain, and give the 2-mSA synthetic PU a unique high backlash elasticity. C. Optionally include a cross-linking agent to increase the cross-linking density of the water-based PU resin and increase the hydrolysis resistance. D. It is especially suitable for the bag and box industry. It needs to use PU with good mechanical properties and high backwash elasticity to increase the delicate feel and meet the green demands of brands such as Detox and ZDHC. Instance

Hereinafter, the present invention will be further described in detail through examples. It is necessary to point out that the following examples are only used to further illustrate the present invention, and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art have made some non-essential improvements and improvements to the present invention based on the above-mentioned content of the present invention. The adjustment still belongs to the protection scope of the present invention. Before discussing several non-limiting embodiments of the present invention, it should be understood that the present invention is not limited in its application to the details of the specific non-limiting embodiments shown and discussed herein, as the present invention may have other embodiments. In addition, the terminology used to discuss the present invention herein is for the purpose of description rather than limitation. Furthermore, unless otherwise specified, the following discussion of similar numbers refers to similar elements.

All numbers expressing content, ratio, physical characteristics, etc. used in this specification and the scope of the patent application should be understood as modified by the term "about" in all cases. Therefore, unless there are instructions to the contrary, the numerical values set forth in the following specification and the scope of the patent application may vary depending on the characteristics sought and/or required by the present invention. At least, and not trying to limit the application of the principle of equivalence to the scope of the patent application, each numerical parameter should at least be explained based on the number of valid digits disclosed and by applying general rounding techniques.

All ranges disclosed in this article should be understood to encompass any and all sub-ranges contained therein. For example, the range of "1 to 10" shall be regarded as including any and all sub-ranges between the minimum value of 1 and the maximum value of 10 and including the maximum value of 1 and the maximum value of 10; All sub-ranges starting with the minimum value of 10 and ending with a maximum value less than 10, for example: 1 to 6.7, 3.2 to 8.1, or 5.5 to 10, and any number in the range, for example: 2.6, 4.7 or 7.3. Example 1

Weigh 200 g of biomass polyester polyol (molecular weight: 1,000, biomass content 50%) that has been vacuum dried and dehydrated, stir evenly and heat to 60°C, weigh out 53.7 g of 1,6-hexamethylene diisocyanate (HDI), add 0.04 g of dibutyltin dilaurate catalyst, keep the temperature at 80°C for polymerization reaction, the reaction time is 2 hours, react until the NCO content reaches the theoretical value to prepare polyurethane prepolymer; wait to be cooled to 50°C Below, add 150 g acetone and 50 g N,N-dimethylformamide to dilute the viscosity of the prepolymer (avoid adding large amounts in a short time to avoid clumping or jamming of the tank wall), and weigh 18.65 g of diaminobenzene sulfonate Sodium, after stirring uniformly for 10 minutes, increase the stirring rate, slowly add 350 g of water dropwise to the polyurethane prepolymer, emulsify for 10 minutes and transfer to the water phase, add 1.73 g of diethylene triamine and 2.05 g of ethylene diamine to confirm After there is no NCO residue, keep the temperature at 30°C, and distill under reduced pressure. After removing the solvent (acetone) for about 1 hour, the biogenic water-based PU is prepared, and 5% by weight (based on the total content of the emulsion ) is added before coating. The aliphatic isocyanate crosslinking agent to improve the hydrolysis resistance of the dry film. The temperature curve and flow of the above reaction are shown in Figure 1. Example 2

Weigh 200 g of biomass polyester polyol (molecular weight: 2,000, biomass content 60%) that has undergone vacuum drying and dehydration, stir evenly and heat to 60°C, weigh 35.46 g of isophorone diisocyanate (IPDI), Keep the temperature at 80°C for polymerization reaction. The reaction time is 3 hours. After the NCO content reaches the theoretical value, the polyurethane prepolymer is prepared; after the temperature is lowered to 50°C, add 260 g of acetone dropwise to dilute the viscosity of the prepolymer (avoid Add a large amount in a short time to avoid clumping or jamming of the tank wall), weigh out 13.66 g of sodium ethylenediaminoethanesulfonate, stir uniformly for 10 minutes, increase the stirring rate, and slowly drop 370 g of water into the polyurethane prepolymer. After emulsifying for 10 minutes and transferring to the water phase, add 4.1 g of isophorone diamine. After confirming that there is no NCO residue, hold the temperature at 30°C, distill under reduced pressure, and extract the solvent (acetone) for about 1 hour. Water-based PU, add 5% by weight (based on the total content of the emulsion ) aliphatic isocyanate crosslinking agent before coating to improve the hydrolysis resistance of the dry film. The temperature curve and flow of the above reaction are shown in Figure 1. Shown. Example 3

Weigh 200 g of biomass polyester polyol (molecular weight: 3,000, biomass content: 55%) and 50 g of polylactone polyol (molecular weight: 2,000) that have been vacuum dried and dehydrated, stir evenly and heat to 60°C, weigh Take 36.43 g of dicyclohexylmethane diisocyanate (HMDI), add 0.03 g of stannous octoate catalyst, keep the temperature at 80 °C for polymerization reaction, the reaction time is 1.5 hours, react until the NCO content reaches the theoretical value to prepare polyurethane prepolymer; After cooling down to below 50°C, add 150 g acetone and 100 g N-methylpyrrolidone dropwise to dilute the viscosity of the prepolymer (avoid adding a large amount in a short time to avoid clumping or jamming of the tank wall), and weigh 13.72 g ethylenediamino Sodium ethanesulfonate, stir evenly for 10 minutes, increase the stirring rate, directly add 425 g of water dropwise to the polyurethane prepolymer, emulsify it for 20 minutes, and then add 1.9 g poly-m-xylylenediamine and 4.5 g diethanolamine. After confirming that there is no residual NCO, keep the temperature at 30°C, and distill under reduced pressure. After removing the solvent (acetone) for about 1.5 hours, the biogenic water-based PU is prepared. Add 5% by weight (based on the total content of the emulsion) before coating. Calculated) Carbimidide crosslinking agent to improve the hydrolysis resistance of the dry film. The temperature curve and flow of the above reaction are shown in Figure 1. Example 4

Weigh 300 g of biomass polyester polyol (molecular weight: 2,000, biomass content 50%), 20 g of dimethylolpropionic acid and 25 g of methyl ethyl ketone, which has been vacuum dried and dehydrated, and stir it evenly and heat to 60°C, Weigh 112.3 g of diphenylmethane 4,4-diisocyanate (MDI), keep the temperature at 85°C for polymerization reaction, the reaction time is 2 hours, and react until the NCO content reaches the theoretical value to prepare polyurethane prepolymer; increase the stirring Add 670 g of water directly to the polyurethane prepolymer. After emulsifying for 10 minutes, add 3.2 g of ethylenediamine and 3.8 g of ethylene glycol to prepare a biogenic water-based PU. Add 5% by weight before coating. The melamine crosslinking agent (based on the total content of the emulsion) is used to improve the hydrolysis resistance of the dry film. The temperature curve and flow of the above reaction are shown in Figure 2. Example 5

Weigh 150 g of biomass polyester polyol (molecular weight: 4,000, biomass content 63%), 100 g of polyether polyol (molecular weight: 2,000) and 11.7 g of dimethylol propionic acid after vacuum drying and dehydration treatment. And heat to 60°C, weigh 19.4 g of toluene diisocyanate (TDI), keep the temperature at 85°C for polymerization reaction, the reaction time is 2.0 hours, and react until the NCO content reaches the theoretical value to prepare the polyurethane prepolymer; increase the stirring Add 580 g of water directly to the polyurethane prepolymer, add 1.5 g of hexamethylene diamine and 3.2 g of methyldiethanolamine to the polyurethane prepolymer after emulsification for 10 minutes, and then add sulfonic acid type waterborne polyurethane emulsion. 5 wt% (based on the total content of the emulsion) of the carbamide crosslinking agent can improve the hydrolysis resistance of the dry film. The temperature curve and flow of the above reaction are shown in FIG. 2. Example 6

Weigh 200 g of biomass polyester polyol (molecular weight: 2,000, biomass content 100%) that has undergone vacuum drying and dehydration, stir evenly and heat to 60°C, weigh 50.54 g of isophorone diisocyanate (IPDI), Keep the temperature at 90°C for polymerization reaction, the reaction time is 3.5 hours, and the NCO content reaches the theoretical value to prepare polyurethane prepolymer; after cooling to below 50°C, 300 g acetone is added dropwise to dilute the viscosity of the prepolymer (avoid Add a large amount in a short time to avoid clumping or jamming of the tank wall), weigh out 18.74 g of sodium aminoalkyl sulfonate, stir evenly for 10 minutes, increase the stirring rate, and slowly drop 328 g of water into the polyurethane prepolymer to emulsify After 10 minutes of transferring to the water phase, add 4.5 g of isophorone diamine, confirm that there is no NCO residue, hold the temperature at 30°C, and distill under reduced pressure. After removing the solvent (acetone) for about 2 hours, the biomass is obtained. For water-based PU, add 5% by weight (based on the total content of the emulsion ) of aliphatic isocyanate crosslinking agent before coating to improve the hydrolysis resistance of the dry film. The temperature curve and flow of the above reaction are shown in Figure 1. Show. Example 7

Coatings Precision Materials Co., Ltd.'s existing sales product (non-biomass water-based PU) was used as a benchmark to evaluate the performance of bio-based water-based PU. Example 8 : Product performance test

i. Determination of solid content

Take the dry watch glass, weigh its weight and mark it as m, then weigh 1.5～2.0 g of the water-based polyurethane emulsion and spread it flat in the watch glass and weigh it as m _0. Place it in an oven and dry at 120°C for 2 hours. Take out the weight and mark it. Is m ₁ , and the solid content is calculated as follows: solid content (%)=[(m ₁ -m)/m ₀ ] x 100% .

ii. 100% film number, tensile strength, and extension ratio are in accordance with the standard test methods ASTM D412 and ASTM D638 .

iii. Hydrolysis resistance The dry film is subjected to the ISO 1419:1995 hydrolysis resistance test (Jungle test), the humidity is 95%, the temperature is 70°C, and the retention of physical properties is tested for one week.

iv. Determination of emulsion stability . Store 100 g of emulsion at room temperature (25°C) and observe every other week whether there is precipitation. The longer it takes to precipitate the precipitation, the better the stability.

v. Elastic response rate According to the standard test method (ASTM D3107) testing method, determine the elastic body length of the garment fabric and its response.

Table 1: Test results of the polyurethane emulsion of the example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Biomass content (%) 36.2 47.6 35.9 34.1 33.1 68.1 0 Solid content (%) 44.1 40.6 41.9 39.6 33.0 42.5 40.5 100% film number (kg/cm ² ) 16.3 25.5 13.7 62.1 55.3 21.0 30.6 Tensile strength (kg/cm ² ) 275 293 188 260 254 203 262 Extension ratio (%) 1241 1356 1513 843 953 1117 908 Hydrolysis resistance (%) ＞83.5 ＞85.6 ＞82.1 ＞83.8 ＞86.1 ＞81.8 ＞88.2 Emulsion stability More than 6 months Elastic recovery rate (%) 95.2 93.6 95.6 91.3 92.2 96.5 88.2 Emulsion appearance Milky white Milky white and blue cream cream cream cream cream

Result analysis: Among the bio-based water-based PU, due to the introduction of 2-mSA in the structure, it has a unique high backlash elasticity, so the elastic recovery rate is better than the existing non-bio-based PU, and the hydrolysis resistance is> 80%, which has met the general sales standards. .

Figure 1 shows the temperature profile and flow of the reactions of Examples 1 to 3. Figure 2 shows the temperature profile and flow of the reactions of Examples 4 and 5.

Claims (16)

A polyurethane, which is prepared from polypolyol and polyisocyanate, wherein the polymerized monomer of the polyester polyol at least contains 2-methylsuccinic acid, and the biomass content of the polyurethane is at least 25%, and According to ASTM D1148, the yellowing resistance level is above 4. The polyurethane of claim 1, wherein the ratio of 2-methylsuccinic acid in the polyester polyol is at least 30 mol% based on the total moles of reactant monomers used to prepare the polyester polyol . The polyurethane of claim 1, wherein the polyester polyol has an APHA color not greater than 30. For example, the polyurethane of claim 1, its hydrolysis resistance tested by the ISO 1419:1995 standard is at least 75%. The polyurethane of claim 1, wherein the polyisocyanate comprises (cyclo)aliphatic diisocyanate, aromatic diisocyanate and/or araliphatic diisocyanate. The polyurethane of claim 1, wherein the polypolyol further comprises a second polyester polyol, polylactone polyol, polyether polyol, polycarbonate polyol, polythioether polyol, polyether and polyester Hybrid polyols, or any mixtures thereof. For example, the polyurethane of claim 1 has a weight average molecular weight of 40,000 to 60,000. Such as the polyurethane of claim 1, its elastic recovery rate tested by ASTM D3107 standard is at least 85%. A method for preparing high-bio-content polyurethane, which comprises the following steps: (1) Provide polyol, polyacid and antioxidant systems; (2) Reaction under nitrogen environment; (3) When the acid value is lower than the first target value, vacuum conditions are applied to the reactor and the reaction continues; (4) The reaction is completed when the acid value is lower than the second target value, and a polyester polyol with high biomass content is produced; (5) React with the high-bio-content polyester polyol, polyisocyanate, optionally-added polypolyol and optionally-added chain extender to prepare high-bio-content polyurethane; The polyol includes at least one alkyl polyol, the polyacid includes at least 2-methylsuccinic acid, and the antioxidant system includes at least two antioxidants. The method of claim 9, wherein step (1) and/or (5) further includes adding a catalyst. The method of claim 9, wherein the ratio of 2-methylsuccinic acid in the polyester polyol is at least 30 mol% based on the total moles of reactant monomers used to prepare the polyester polyol. The method of claim 9, wherein the oxidant comprises a phosphite antioxidant and a hindered amine compound antioxidant. The method of claim 9, wherein the polyisocyanate comprises (cyclo)aliphatic diisocyanate, aromatic diisocyanate and/or araliphatic diisocyanate. The method of claim 9, wherein the optionally added polypolyol comprises a second polyester polyol, polylactone polyol, polyether polyol, polycarbonate polyol, polythioether polyol, polyether and Polyester hybrid polyols, or any mixtures thereof. The method of claim 9, wherein the optionally added chain extender includes ethylene glycol, hexylene glycol, ethylene diamine, hexamethylene diamine, phenylene diamine, diethanolamine, polyoxypropylene triamine, and diethylene triamine , Isophorone diamine, m-xylylenediamine, methyldiethanolamine, or any mixtures thereof. Such as the method of claim 9, wherein step (5) further includes the following steps: (a) React the high biomass content polyester polyol, polyisocyanate, and optionally added polypolyol to form a polyurethane prepolymer; and (b) Reacting the polyurethane prepolymer with the chain extender to form polyurethane with high biomass content.

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