CN111748310B - Double-component polyurethane adhesive and preparation method thereof - Google Patents

Abstract

The invention provides a double-component polyurethane adhesive and a preparation method thereof, wherein the double-component polyurethane adhesive comprises a component A and a component B; the component A consists of the following raw materials in parts by weight: 45-56.2 parts of polyether polyol, 40-50.4 parts of filler A and 0.4-0.6 part of catalyst; the component B comprises the following raw materials in parts by weight: 30-37 parts of polyurethane prepolymer, 7.8-22 parts of polyisocyanate, 0-13 parts of plasticizer and 30-44 parts of filler B; the polyurethane prepolymer is a compound containing terminal isocyanate group and prepared from prepolymer polyether polyol, prepolymer polyisocyanate, a synthetic catalyst and a plasticizer. The invention has the beneficial effects that: the double-component polyurethane adhesive provided by the invention has good thixotropy and rapid strength increase performance; the double-component polyurethane adhesive provided by the invention is only used according to the proportion of 1.

Description

Double-component polyurethane adhesive and preparation method thereof

Technical Field

The invention belongs to the field of polyurethane adhesives, and particularly relates to a two-component polyurethane adhesive and a preparation method thereof.

Background

The main material of the single-component moisture-curing polyurethane sealant contains isocyanate-terminated groups, and can react with moisture in the air at room temperature to form a high-strength elastomer. The sealant has good mechanical and physical properties, chemical corrosion resistance, water resistance, low temperature resistance, vibration and impact resistance and other properties, so that the sealant is widely applied to bonding of automobile windshield glass. However, the curing process of the single-component product is long, the strength needs a certain time to rise, and the single-component product is greatly influenced by temperature and humidity, so that the curing process is one of important bottlenecks in accelerating the production speed of a modern industrialized production line.

Although the bi-component polyurethane adhesive product can avoid the influence of the curing process of a single-component product, the bi-component polyurethane adhesive is suitable for the defects of insufficient elasticity and poor thixotropy existing in structural bonding; the product suitable for encapsulation and sealing has poor mechanical property and can not meet the standard requirement of the automobile windshield glass bonding industry. In recent years, the developed two-component polyurethane windshield glass adhesive is mainly a catalytic curing system, wherein the component A is common one-component polyurethane, the component B is a substance containing active hydrogen or free water molecules, and the use ratio is 10-50. Although the bonding requirement of the windshield glass can be met, due to the fact that the proportion of the AB component is greatly different, the high requirement is placed on sizing equipment, and the phenomenon that the curing speed of a product is different due to the fact that the proportion is out of control can occur.

Therefore, the two-component polyurethane adhesive is urgently needed to be developed to avoid the performance defects, meet the industrial standard and meet the requirements of an automobile windshield glass assembly line.

Disclosure of Invention

The invention provides a two-component polyurethane adhesive and a preparation method thereof, aiming at solving the technical problem that the two-component polyurethane adhesive for windshield glass in the prior art cannot meet the requirements of an assembly line of automobile windshield glass because the use amounts of the A component and the B component are greatly different when in use.

The specific technical scheme is as follows:

a double-component polyurethane adhesive is characterized by comprising a component A and a component B;

the component A consists of the following raw materials in parts by weight:

45 to 56.2 portions of polyether polyol, 40 to 50.4 portions of filler A and 0.4 to 0.6 portion of catalyst;

the component B comprises the following raw materials in parts by weight:

30-37 parts of polyurethane prepolymer, 7.8-22 parts of polyisocyanate, 0-13 parts of plasticizer and 30-44 parts of filler B;

the polyurethane prepolymer is a compound containing terminal isocyanate group and prepared from prepolymer polyether polyol, prepolymer polyisocyanate, a synthetic catalyst and a plasticizer.

Further, the polyether polyol comprises:

polyether glycol: 8-23 parts of polyether triol: 26-47 parts;

the relative molecular mass of the polyether glycol is 400-2000, and the hydroxyl value is 50-300 mgKOH/g;

the relative molecular mass of the polyether triol is 1000-6000, and the hydroxyl value is 28 mgKOH/g-168 mgKOH/g.

Further, the filler A is one or more of nano calcium carbonate, calcined kaolin, calcium carbonate or talcum powder; the filler B is one or more of carbon black, calcined kaolin, calcium carbonate or talcum powder.

Further, the catalyst is one or more of dibutyltin dilaurate, dioctyltin dilaurate, dimorpholinodiethyl ether or bismuth isooctanoate; the synthetic catalyst is stannous octoate.

Further, the prepolymer polyisocyanate is 4,4' -diphenylmethane diisocyanate.

Further, the prepolymerization polyether polyol is selected from polyether polyols with the average molecular weight of 4800-6000 and three functionality degrees.

Further, the plasticizer is selected from one or more of dioctyl phthalate, diisodecyl phthalate or diisononyl phthalate.

Further, the polyisocyanate includes one or more selected from diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, or toluene diisocyanate.

Further, the polyurethane prepolymer is a compound containing terminal isocyanate group and prepared from 70-80 parts by weight of prepolymer polyether polyol, 10-15 parts by weight of prepolymer polyisocyanate, 0.05-0.1 part by weight of synthetic catalyst and 5-15 parts by weight of plasticizer, and the polyurethane prepolymer accounts for 29-38% of the component B by weight.

The preparation method of the double-component polyurethane adhesive is characterized by comprising the following steps:

preparing a component A:

adding polyether polyol and a filler A into a reactor, heating, dehydrating, cooling, adding a catalyst, and stirring to obtain a component A;

preparing a component B:

preparing a polyurethane prepolymer;

and adding the polyurethane prepolymer, polyisocyanate and the filler B into a reactor, and stirring for 1-3 hours in vacuum to prepare a component B.

Compared with the prior art, the invention has the beneficial effects that:

(1) The double-component polyurethane adhesive provided by the invention has good thixotropy and rapid strength increase performance;

(2) The volume ratio of the two-component polyurethane adhesive provided by the invention is 1 (0.95-1.05), and the flow line operation of the automobile windshield can be met.

Detailed Description

The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.

A two-component polyurethane adhesive is characterized in that the two-component polyurethane comprises a component A and a component B;

the component A consists of the following raw materials in parts by weight:

45 to 56.2 portions of polyether polyol, 40 to 50.4 portions of filler A and 0.4 to 0.6 portion of catalyst;

the component B comprises the following raw materials in parts by weight:

30-37 parts of polyurethane prepolymer, 7.8-22 parts of polyisocyanate, 0-13 parts of plasticizer and 30-44 parts of filler B;

the polyurethane prepolymer is a compound containing terminal isocyanate, which is prepared from prepolymer polyether polyol, prepolymer polyisocyanate, a synthetic catalyst and a plasticizer;

the polyurethane prepolymer accounts for 29-38% of the component B by mass.

In the term of the two-component polyurethane, the polyurethane is generally divided into two parts, one group of reaction substances is polyurethane prepolymer, and the other group is polyol, and when the two-component polyurethane is used, the polyurethane prepolymer and the polyol react to carry out crosslinking and curing;

the term "polyurethane prepolymer" refers to a high molecular polymer terminated with polyisocyanate, which is obtained by reacting polyether polyol with polyisocyanate at a certain temperature under the action of a suitable synthesis catalyst, and is in a stable state at a certain temperature, and then, under the action of the catalyst, the high molecular polymer and activated hydrogen undergo a polymerization reaction.

The prepolymer polyisocyanate is 4,4' -diphenylmethane diisocyanate, and the prepolymer polyether polyol is selected from polyether polyol with the average molecular weight of 4800-6000 and the three-functionality degree and is selected from one of EP3600, GEP-330N, wanolF3135 and WanolF 3128;

further optimized, the NCO content of the polyurethane prepolymer synthesized by the invention is 1.0-3.0%, and the rotational viscosity is 7000 mPa.s-60000mPa.s.

Specifically, the polyurethane prepolymer is a compound containing terminal isocyanate group, which is prepared from 70-80 parts by weight of prepolymer polyether polyol, 10-15 parts by weight of prepolymer polyisocyanate, 0.05-0.1 part by weight of synthetic catalyst and 5-15 parts by weight of plasticizer.

The 'synthetic catalyst' in the invention refers to a catalyst for the reaction of polyisocyanate and polyether polyol, and the synthetic catalyst is stannous octoate;

in the invention, the component B is polyisocyanate and polyurethane prepolymer, and when the polyurethane prepolymer and the polyisocyanate are used, the polyurethane prepolymer and polyether polyol react simultaneously.

In the present invention, the plasticizer is selected from one or more of dioctyl phthalate (DOP), diisodecyl phthalate (DIDP) or diisononyl phthalate (DINP).

In the invention, the component A polyether polyol is used for extracting partial activated hydrogen for reacting with the component B polyurethane prepolymer and polyisocyanate, and the polyether polyol in the component A comprises:

polyether glycol: 8-23 parts of polyether triol: 26-47 parts;

the relative molecular mass of the polyether glycol is 400-2000, and the hydroxyl value is 50-300 mgKOH/g;

the relative molecular mass of the polyether triol is 1000-6000, and the hydroxyl value is 28 mgKOH/g-168 mgKOH/g.

Further, the polyether polyol in the component A is selected from polyether diol (DL-2000), polyether diol (DL-400) and polyether triol (T700);

or

Polyether diol (DL-400), polyether triol (WanolF 3135), polyether triol (T700); the performance is more excellent, especially in the surface dry time.

In the invention, the term "filler" is used for ensuring the mechanical strength, increasing the thixotropy and reducing the cost, and the filler A is one or more of nano calcium carbonate, calcined kaolin, coarse whiting or talcum powder; the filler B is one or more of carbon black, calcined kaolin, heavy calcium or talcum powder.

The catalyst is used for catalyzing and promoting the crosslinking reaction of the polyurethane sealant prepolymer and activated hydrogen, and is one or more of dibutyltin dilaurate, dioctyltin dilaurate, dimorpholinyl diethyl ether or bismuth isooctanoate;

further, the polyisocyanate includes one or more selected from diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, or toluene diisocyanate.

The preparation method of the double-component polyurethane adhesive is characterized by comprising the following steps:

preparing a component A:

adding polyether polyol and a filler A into a reactor, heating to 100-120 ℃, carrying out vacuum stirring dehydration for 1-3 hours, then cooling to 55-65 ℃, adding a catalyst, and carrying out vacuum stirring for 0.5 hour to obtain a component A;

preparing a component B:

preparation of polyurethane prepolymer: the polyurethane prepolymer is prepared by reacting prepolymer polyisocyanate, prepolymer polyether polyol and plasticizer at 80 +/-5 ℃ under the action of a synthetic catalyst for 2-5 h, cooling, discharging, and filling into a closed container for later use.

And adding the polyurethane prepolymer, polyisocyanate and the filler B into a reactor, and stirring for 1-3 hours in vacuum to prepare a component B.

Example 1

The preparation steps of the component A are as follows: adding polyether diol (DL-400), polyether triol (WanolF 3128) and nano calcium carbonate into a three-neck flask, adding into a planetary stirring mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of-0.9 MPa, then cooling to 60 ℃, adding 0.35 part of bismuth isooctanoate, stirring for 30 minutes under the condition of vacuum degree of-0.9 MPa, and discharging to obtain the component A.

The preparation steps of the component B are as follows: adding DOP and polyether triol EP-3600 into a dry three-neck flask, vacuumizing and dehydrating for 0.5-1 h at 120 ℃, cooling to about 60 ℃, adding metered 4,4' -diphenylmethane diisocyanate and stannous octoate, slowly heating to 80 ℃, carrying out heat preservation reaction for 3h under the protection of dry nitrogen, cooling and discharging to obtain the polyurethane prepolymer I.

Adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer I, carbon black, calcined kaolin and a plasticizer, stirring and stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain a component B.

According to the formula A: b =1 (volume ratio) was thoroughly mixed and used.

TABLE 1 example 1A Components raw materials and parts by weight

Raw materials	Parts by weight
		DL-400 (polyether glycol)	10.0
WanolF3128 (polyether triol)	46.2
		Nano calcium carbonate (Filler A)	43.35
Bismuth isooctanoate (catalyst)	0.45

TABLE 2 polyurethane prepolymer I raw materials and parts by weight

TABLE 3 example 1B Components, raw materials and parts by weight

Raw materials	Parts by weight
		Wanhua chemical MDI-50 (polyisocyanate)	7.8
Polyurethane prepolymers I	37
		Carbon black (Filler B)	15
Kaolin (Filler B)	29.5
		DINP (plasticizer)	10.7

Example 2

The preparation steps of the component A are as follows: adding polyether diol (DL-2000), polyether triol (T700), nano calcium carbonate and talcum powder into a three-neck flask, adding into a planetary stirring dynamic mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is-0.9 MPa, then cooling to 60 ℃, adding dibutyltin dilaurate, stirring for 30min under the condition that the vacuum degree is-0.9 MPa, and discharging to obtain the component A.

The preparation step of the component B comprises the following steps: adding a plasticizer and polyether triol Walol F3135 into a dry three-neck flask, vacuumizing and dehydrating for 0.5-1 h at 120 ℃, cooling to about 60 ℃, adding metered 4,4' -diphenylmethane diisocyanate and stannous octoate, slowly heating to 80 ℃, reacting for 3h under the protection of dry nitrogen, cooling and discharging to obtain the polyurethane prepolymer II.

Adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer II, carbon black and calcium carbonate, stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain the component B.

According to the formula A: b =1 (volume ratio) and can be used after being fully mixed.

TABLE 4 example 2A Components raw materials and parts by weight

Starting materials	Parts by weight
		DL-2000 (polyether diol)	23
T700 (polyether triol)	26
		Nano calcium carbonate (Filler A)	35.5
Talcum powder (Filler A)	14.9
		Dibutyltin dilaurate (catalyst)	0.6

TABLE 5 polyurethane prepolymer II raw materials and parts by weight

TABLE 6 example 2B Components, raw materials and parts by weight

Starting materials	Parts by weight
		Wanhua chemical MDI-50 (polyisocyanate)	21.5
Polyurethane prepolymers II	37.0
		Carbon black (Filler B)	20.2
Calcium carbonate (Filler B)	21.3

Example 3

The preparation steps of the component A are as follows: adding polyether diol (DL-2000), polyether diol (DL-400), polyether triol (T700) and nano calcium carbonate into a three-neck flask, adding into a planetary stirring dynamic mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of-0.9 MPa of vacuum degree, then cooling to 60 ℃, adding bismuth isooctanoate, stirring for 30 minutes under the condition of-0.9 MPa of vacuum degree, and discharging to obtain the component A.

The preparation steps of the component B are as follows: adding DOP and polyether triol EP-3600 into a dry three-neck flask, vacuumizing and dehydrating for 0.5-1 h at 120 ℃, cooling to about 60 ℃, adding metered 4,4' -diphenylmethane diisocyanate and stannous octoate, slowly heating to 80 ℃, carrying out heat preservation reaction for 3h under the protection of dry nitrogen, cooling and discharging to obtain the polyurethane prepolymer III.

Adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer III, carbon black, kaolin and a plasticizer, stirring and stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain the component B.

TABLE 7 example 3A Components raw materials and parts by weight

Starting materials	Parts by weight
		DL-2000 (polyether glycol)	15.0
DL-400 (polyether glycol)	8.0
		T700 (polyether triol)	26.0
Nano calcium carbonate (Filler A)	41.55
		Bismuth isooctanoate (catalyst)	0.45

TABLE 8 polyurethane prepolymer III raw materials and parts by weight

TABLE 9 example 3B Components raw materials and parts by weight

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Example 4

The preparation steps of the component A are as follows: adding polyether diol (DL-400), polyether triol (WanolF 3135), polyether triol (T700), talcum powder and nano calcium carbonate into a three-neck flask, adding into a planetary stirring dynamic mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of-0.9 MPa, then cooling to 60 ℃, adding dibutyltin dilaurate, stirring for 30 minutes under the condition of vacuum degree of-0.9 MPa, and discharging to obtain the component A.

The preparation steps of the component B are as follows: adding a plasticizer and polyether triol Walol F3135 into a dry three-neck flask, vacuumizing and dehydrating for 0.5-1 h at 120 ℃, cooling to about 60 ℃, adding metered 4,4' -diphenylmethane diisocyanate and stannous octoate, slowly heating to 80 ℃, carrying out heat preservation reaction for 3h under the protection of dry nitrogen, cooling and discharging to obtain the polyurethane prepolymer IV.

Adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer IV, carbon black, kaolin and plasticizer, stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain the component B.

According to the formula A: b =1 (volume ratio) and can be used after being fully mixed.

TABLE 10 example 4A Components raw materials and parts by weight

TABLE 11 polyurethane prepolymer IV raw materials and parts by weight

TABLE 12 example 4 part by weight of B Components

Raw materials	Parts by weight
		Wanhua chemical MDI-50 (polyisocyanate)	11.0
Polyurethane prepolymer IV	32.0
		Carbon black (Filler B)	21.0
Kaolin (Filler B)	23.0
		DINP (plasticizer)	13.0

Example 5

The preparation steps of the component A are as follows: adding polyether diol (DL-400), polyether triol (WanolF 3128) and nano calcium carbonate into a three-neck flask, adding into a planetary stirring mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of-0.9 MPa, then cooling to 60 ℃, adding 0.35 part of bismuth isooctanoate, stirring for 30 minutes under the condition of vacuum degree of-0.9 MPa, and discharging to obtain the component A.

The preparation steps of the component B are as follows: adding Wanhua chemical MDI-50 into a planetary stirrer, adding polyurethane prepolymer I, carbon black and calcined kaolin, stirring and stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain a component B.

According to the formula A: b =1 (volume ratio) was thoroughly mixed and used.

TABLE 13 example 5A Components raw materials and parts by weight

Raw materials	Parts by weight
		DL-400 (polyether glycol)	16.2
WanolF3128 (polyether triol)	38.8
		Nano calcium carbonate (Filler A)	40
Bismuth isooctanoate (catalyst)	0.4

TABLE 14 example 5B Components raw materials and parts by weight

Raw materials	Parts by weight
		Wanhua chemical MDI-50 (polyisocyanate)	10
Polyurethane prepolymers I	30.0
		Carbon black (Filler B)	22
Kaolin (Filler B)	8.0
		DINP (plasticizer)	10

Comparative example 1

The preparation steps of the component A are as follows: adding polyether diol (DL-400), polyether triol (WanolF 3128), nano calcium carbonate, 1, 4-butadiene (chain extender) and triethanolamine (chain extender) into a three-neck flask, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of-0.9 MPa, cooling to 60 ℃, adding bismuth isooctanoate, stirring for 30 minutes under the condition of vacuum degree of-0.9 MPa, and discharging to obtain the component A.

The preparation steps of the component B are as follows:

adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer I, carbon black, kaolin and a plasticizer, stirring and stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain a component B.

According to the formula A: b =1 (volume ratio) was thoroughly mixed and used.

TABLE 15 comparative example 1A Components raw materials and parts by weight

Starting materials	Parts by weight
		DL-400 (polyether glycol)	10.0
WanolF3128 (polyether triol)	46.2
		1, 4-butadiene (chain extender)	3
Triethanolamine (chain extender)	1.0
		Nano calcium carbonate (Filler A)	39.35
Bismuth isooctanoate (catalyst)	0.45

TABLE 16 raw materials and weight parts of comparative example 1B component

Raw materials	Parts by weight
		Wanhua chemical MDI-50 (polyisocyanate)	7.8
Polyurethane prepolymers I	37
		Carbon black (Filler)	15
Kaolin (Filler)	29.5
		DINP (plasticizer)	10.7

Comparative example 2

The preparation steps of the component A are as follows: adding polyether diol (DL-400), polyether triol (WanolF 3128) and nano calcium carbonate into a three-neck flask, adding into a planetary stirring mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of-0.9 MPa, then cooling to 60 ℃, adding 0.35 part of bismuth isooctanoate, stirring for 30 minutes under the condition of vacuum degree of-0.9 MPa, and discharging to obtain the component A.

The preparation steps of the component B are as follows: adding DOP and polyether triol EP-3600 into a dry three-neck flask, vacuumizing and dehydrating for 0.5-1 h at 120 ℃, cooling to about 60 ℃, adding metered 4,4' -diphenylmethane diisocyanate and stannous octoate, slowly heating to 80 ℃, carrying out heat preservation reaction for 3h under the protection of dry nitrogen, cooling and discharging to obtain the polyurethane prepolymer I.

Adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer I, carbon black, calcined kaolin and a plasticizer, stirring and stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain a component B.

According to the formula A: b =1 (volume ratio) and can be used after being fully mixed.

TABLE 17 COMPARATIVE EXAMPLE 2A COMPONENT MATERIAL AND ITS WEIGHT PARTS

Raw materials	Parts by weight
		DL-400 (polyether glycol)	10.0
WanolF3128 (polyether triol)	46.2
		Nano calcium carbonate (Filler A)	43.35
Bismuth isooctanoate (catalyst)	0.45

TABLE 18 polyurethane prepolymer I raw materials and parts by weight

Raw materials	Parts by weight
		DOP (plasticizer)	10
EP-3600 (polyether polyol)	76.45
		4,4' -diphenylmethane diisocyanate	13.5
Stannous octoate (synthetic catalyst)	0.05

TABLE 19 raw materials and weight parts of comparative example 2B component

Starting materials	Parts by weight
		Wanhua chemical MDI-50 (polyisocyanate)	6
Polyurethane prepolymers I	42
		Carbon black (Filler)	15
Kaolin (Filler)	29.5
		DINP (plasticizer)	7.5

Comparative example 3

The preparation steps of the component A are as follows: adding dioctyl phthalate, 2000-molecular-weight polyether diol and 5000-molecular-weight polyether triol into a dry three-neck flask, vacuumizing and dehydrating at 120 ℃ for 4 hours, cooling to about 85 ℃, adding metered diphenylmethane diisocyanate, carrying out heat preservation reaction under the protection of dry nitrogen for 2 hours, cooling and discharging to obtain the polyurethane prepolymer V.

Adding a polyurethane prepolymer V and polymethylene polyphenyl polyisocyanate into a planetary stirrer, stirring for 30min at the temperature of 45 ℃ in vacuum, adding dried carbon black, active calcium carbonate and heavy calcium carbonate, mixing and stirring for 2h, adding bismuth isooctanoate, N-phenyl-gamma-aminopropyltrimethoxysilane and oxazolidine water removal agents, stirring and stirring for 1h at the temperature of 45 ℃, and discharging to obtain the component A.

The preparation steps of the component B are as follows:

adding 5000 molecular weight polyether triol, castor oil polyalcohol, polyester dihydric alcohol, carbon black, activated calcium carbonate, dioctyl phthalate and 1, 4-butanediol into a planetary mixer, stirring and stirring for 4 hours under the conditions that the vacuum degree is-0.9Mpa and the temperature is 95 ℃, introducing cooling water to control the temperature to be below 45 ℃, adding bismuth isooctanoate and N-phenyl-gamma-aminopropyltrimethoxysilane, stirring for 1.5 hours under the protection of nitrogen, and discharging to obtain a component B.

According to the formula A: b =1 (volume ratio) was thoroughly mixed and used.

TABLE 20 polyurethane prepolymer V raw materials and parts by weight

Starting materials	Parts by weight
		2000 molecular weight polyether diols	18.87
5000 molecular weight polyether triol	49.06
		Dioctyl phthalate	18.86
Diphenylmethane diisocyanate	13.21

TABLE 21 comparative example 3A Components raw materials and parts by weight

TABLE 22 COMPARATIVE EXAMPLE 3B COMPONENT MATERIAL AND ITS WEIGHT PARTS

Raw materials	Parts by weight
		5000 molecular weight polyether triols	33.81
Castor oil polyols	9.22
		Polyester diol	8.20
Carbon black	15.37
		Activated calcium carbonate	8.20
Dioctyl phthalate	21.51
		1, 4-butanediol	3.07
Bismuth Isooctanoate	0.31
		N-phenyl-gamma-aminopropyltrimethoxysilane	0.31

Example 6

And (4) performance testing: the test was carried out according to "HG/T4363-2012 Single-component polyurethane adhesive for automotive glazings".

The results are shown in tables 23 and 24:

table 23 shows the results of the performance tests of examples

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1 refers to the density of the mixed two-component polyurethane

The Tn 2 two-component polyurethane is different from the standard description of the curing depth of the one-component polyurethane, and the thickness of a glue layer can be completely cured within 24 hours.

Table 24 shows the results of the test of comparative examples

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1 refers to the density of the mixed two-component polyurethane

Tn 2 two-component polyurethane is different from the standard description of the curing depth of one-component polyurethane, and the thickness of a glue layer can be completely cured within 24 hours.

As can be seen from the test results, the examples have significant advantages over the comparative examples in terms of elastic properties such as hardness and elongation at break, and the adhesive for automotive windshields is effective in joining windshields to vehicle bodies, and not only requires good adhesion and aging resistance, but also has elastomeric characteristics, effectively avoiding vibration fatigue during vehicle travel and avoiding stress concentration due to the shape of windshields and vehicle bodies. In the embodiment, the mechanical property is ensured, meanwhile, the hardness control and the elongation at break are considered, and the elasticity of the windshield glass cement is ensured.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. The two-component polyurethane adhesive is characterized by comprising a component A and a component B, wherein the volume ratio of the component A to the component B is 1: (0.95 to 1.05);

the component A consists of the following raw materials in parts by weight:

45-56.2 parts of polyether polyol, 40-50.4 parts of filler A and 0.4-0.6 part of catalyst, wherein the polyether polyol comprises: polyether glycol: 8-23 parts of polyether triol: 26-47 parts; the relative molecular mass of the polyether glycol is 400-2000, and the hydroxyl value is 50-300 mgKOH/g; the relative molecular mass of the polyether triol is 1000-6000, and the hydroxyl value is 28 mgKOH/g-168 mgKOH/g;

the component B comprises the following raw materials in parts by weight:

30-37 parts of polyurethane prepolymer, 7.8-22 parts of polyisocyanate, 0-13 parts of plasticizer and 30-44 parts of filler B;

the polyurethane prepolymer is a compound containing terminal isocyanate groups, wherein the compound is prepared from 70-80 parts of prepolymer polyether polyol, 10-15 parts of prepolymer polyisocyanate 4,4' -diphenylmethane diisocyanate, 0.05-0.1 part of synthetic catalyst stannous octoate and 5-15 parts of plasticizer, and the prepolymer polyether polyol is selected from polyether polyols with the average molecular weight of 4800-6000 and the trifunctional degree.

2. The two-component polyurethane adhesive of claim 1, wherein the filler A is one or more of nano calcium carbonate, calcined kaolin, calcium carbonate or talc; the filler B is one or more of carbon black, calcined kaolin, calcium carbonate or talcum powder.

3. The two-component polyurethane adhesive of claim 1, wherein the catalyst is one or more of dibutyltin dilaurate, dioctyltin dilaurate, dimorpholinodiethylether, or bismuth isooctanoate.

4. The two-component polyurethane adhesive of claim 1, wherein the plasticizer is selected from one or more of dioctyl phthalate, diisodecyl phthalate, or diisononyl phthalate.

5. The two-component polyurethane adhesive of claim 1, wherein the polyisocyanate is selected from one or more of diphenylmethane diisocyanate and toluene diisocyanate.

6. The two-component polyurethane adhesive of claim 1, wherein the mass ratio of the polyurethane prepolymer to the component B is 29-38%.

7. The preparation method of the two-component polyurethane adhesive of any one of claims 1 to 6, which is characterized by comprising the following steps:

preparing a component A:

adding polyether polyol and a filler A into a reactor, heating, dehydrating, cooling, adding a catalyst, and stirring to obtain a component A;

preparing a component B:

preparing a polyurethane prepolymer;

and adding the polyurethane prepolymer, polyisocyanate and the filler B into a reactor, and stirring for 1 to 3 hours in vacuum to prepare a component B.